JP7111260B2 - Heat-sensitive adhesive sheet and method for producing article laminated with heat-sensitive adhesive sheet - Google Patents

Description

TECHNICAL FIELD The present invention relates to a heat-sensitive adhesive sheet and a method for manufacturing an article laminated with the heat-sensitive adhesive sheet.

For the purpose of imparting design and functionality to the surface of molded products, decorative layers (hereinafter referred to as , a decorative layer), or a functional layer (hereinafter referred to as a functional layer) with metal wiring such as a touch sensor element and an antenna wire is laminated. For the purpose of protecting the surfaces of these decorative layers and functional layers from scratches, deterioration, corrosion, etc., the surface layers of these decorative layers and functional layers are laminated with thermoplastic materials such as polycarbonate resins and acrylic resins. be done. Furthermore, a hard coat layer, a mat layer, an ultraviolet absorption layer, an antistatic layer, or the like can be laminated on the surface of the thermoplastic lamination material. can effectively protect the decorative layer and the functional layer from damage caused by In addition, if the decorative layer and the functional layer are laminated on the back side of the thermoplastic lamination material in advance and then laminated to the surface of the molded article, lamination is easier than in the case of directly laminating them on the surface of the molded article. It can be performed.

As a method for laminating the thermoplastic laminating material and the molded product, for example, only the thermoplastic laminating material is softened by heating at about 90 ° C. to 200 ° C. for about 1 second to 300 seconds, and placed in a reduced pressure space. Compressed air molding machine or vacuum molding that presses strongly against the surface of an object with compressed air or the like, deforms the heated thermoplastic lamination material in a three-dimensional direction, and attaches and adheres it so as to follow the shape of the surface of the molded object. A bonding method using a machine, a TOM molding machine, or the like is used (for example, Patent Document 1).

However, in the method of heating the thermoplastic pasting material above the temperature at which stickiness occurs and pasting it onto the surface of the molded product, the surface of the thermoplastic pasting material is also softened, and appearance defects such as uneven luster and waviness are likely to occur. . Therefore, a method is used in which an adhesive layer is sandwiched between the thermoplastic bonding material and the molded article to lower the heating temperature during molding of the thermoplastic bonding material.

As the adhesive layer, for example, a liquid adhesive that undergoes a curing reaction with stimulation energy such as heat, moisture, or ultraviolet rays is used (eg, Patent Document 2). However, when using a liquid adhesive that cures with heat or humidity, it takes about 24 hours to harden after the thermoplastic bonding material is bonded to the surface of the molding. In addition, when using a liquid adhesive that cures with ultraviolet rays, light transmission is inhibited by shields such as the decorative layer on the back of the thermoplastic laminating material and the ultraviolet absorption layer, which inhibits ultraviolet curing and causes insufficient curing. likely to occur. Therefore, during the period until the liquid adhesive is cured and the thermoplastic bonding material is fixed, the thermoplastic bonding material that has been deformed in the three-dimensional direction will not lift or peel off from the end portion due to the curved surface repulsive force. There is a problem that the liquid adhesive flows and overflows, and the thickness of the adhesive layer is easily changed. Furthermore, when the liquid adhesive is heated to about 90° C. to 200° C. while being laminated with the thermoplastic bonding material, there is a problem that the liquid adhesive tends to form air bubbles due to the gas generated from the thermoplastic bonding material due to heating. .

Also, instead of liquid adhesives, thermosetting or ultraviolet-curing adhesive sheets containing polymerizable monomer or oligomer components are sometimes used. These adhesive sheets are less likely to float or peel off from the edges, protrude from the laminated product due to flow, or change in thickness, unlike the liquid adhesive described above. When the adhesive layer is heated to about 90°C to 200°C while being laminated with the composite material, the polymerizable monomer or oligomer component significantly softens the adhesive layer, and the adhesive sheet is softened by the gas generated from the thermoplastic laminating material. There was a problem that it is easy to form air bubbles.

If a non-curable pressure-sensitive adhesive sheet containing no polymerizable monomer or oligomer component is used, the above problem can be solved, but the sheet is left in a hot and humid environment of 85° C. and 85% RH for a long period of time. When at least one of the thermoplastic lamination material and the molded product is capable of generating gas, the pressure of the generated gas deforms the adhesive layer over time, and the adhesive sheet forms bubbles or peels off. there was a problem with

For example, grooves are provided to release gas generated from the thermoplastic lamination material or molded product from the interface of the adhesive layer to the surroundings (for example, Patent Document 3), or fine pores are provided on the surface of the thermoplastic lamination material. In this case, these grooves and pores remain even after heat lamination, resulting in poor appearance. In addition, in order to suppress the generation of gas from the surface of the thermoplastic bonding material and the molded product after bonding, a step of preheating these adherends to release gas is required (for example, Patent Document 4). It was inferior in production efficiency.

In addition, when the liquid adhesive or adhesive sheet is used, it is highly sticky at room temperature, so it is difficult to correct the position when attaching to a laminating device such as a pressure forming machine, a vacuum forming machine, or a TOM forming machine. In addition, there is also the problem that dirt and foreign substances adhere to the surface of the adhesive, and the appearance after lamination is impaired. Furthermore, when the thermoplastic lamination material is first molded so as to conform to the shape of the molded product and then laminated to the surface of the molded product with the liquid adhesive or adhesive sheet, the stickiness is high at room temperature, so the bonding position There are also problems such as slippage and inclusion of air bubbles in the lamination interface.
When using a hot-melt heat-sensitive adhesive or heat-sensitive adhesive sheet that does not contain a polymerizable monomer or oligomer component, is solid and non-sticky below 90°C, and softens between 90°C and 200°C, the above problems can be solved. However, it lacks flexibility in low-temperature environments, so it is used in cold environments below 0 ° C, such as in automobiles, and in applications where cold and heat are repeated, such as home appliances and mobile terminals. There was a problem that the adhesive layer could not completely relax the strain caused by the difference in expansion between the bonding material and the molding, and the thermoplastic bonding material and the molding tended to separate or separate.

JP 2015-145103 A JP 2015-072343 A JP 2011-016258 A JP 2014-205335 A

The problem to be solved by the present invention is that in the step of heating a thermoplastic bonding material or the like to about 90 ° C. to 200 ° C. and bonding it to the surface of a molded product or the like while deforming it in a three-dimensional direction, the thermoplastic bonding material By suppressing the formation of air bubbles due to gas generated from such materials and peeling due to repulsion from the curved surface of the thermoplastic lamination material, it is possible to realize adhesion between the thermoplastic lamination material and the molded product. Even if it is left in a hot and humid environment, it suppresses the formation and peeling of bubbles due to gas that can be generated from at least one of the thermoplastic lamination material and the molded product. A heat-sensitive adhesive sheet that can suppress lifting and peeling between a thermoplastic lamination material and a molded product even when An object of the present invention is to provide a method for manufacturing an article that can realize a laminated product with.

The present inventors have found that the above problems can be solved by a heat-sensitive adhesive sheet having a heat-sensitive adhesive layer with various tensile elastic moduli and a bonding method using the heat-sensitive adhesive sheet.
That is, in the present invention, the peak temperature of the tensile loss tangent (tan δ) measured at a frequency of 3 Hz within the range of -50 ° C. to 200 ° C. is at least one above 90 ° C. and at least below -20 ° C. a thermal adhesive layer (a) having one or more and having a tensile storage modulus (E′ _a100 ) at 100° C. of 5×10 ⁵ Pa to 1×10 ⁸ Pa; A heat-sensitive adhesive sheet (A) used for laminating a thermoplastic laminating material (B) as a layer to the surface of a molding (C) is provided.

The heat-sensitive adhesive sheet of the present invention uses a specific heat-sensitive adhesive sheet as an adhesive layer for adhering the thermoplastic laminating material and the like to the molded article, etc., so that the thermoplastic laminating material and the like can be heated at 90°C to 90°C. In the process of heating to about 200 ° C and laminating while deforming the surface of the molded product in a three-dimensional direction, the formation of bubbles due to gas that can be generated from the thermoplastic laminating material, etc., and the repulsion of the curved surface of the thermoplastic laminating material, etc. It is possible to achieve adhesion between the thermoplastic lamination material and the molded product, which suppresses the peeling caused by the adhesion. Further, the heat-sensitive adhesive sheet of the present invention, even if the laminated product of the thermoplastic laminated material and the like is left in a hot and humid environment, the thermoplastic laminated material and the like or the molded article etc. Heat that suppresses the formation and peeling of bubbles due to gas that may be generated, and suppresses the lifting and peeling between the thermoplastic pasting material, etc. and the molded product, etc. It is possible to realize a laminated product of a plastic laminated material or the like and a molded product or the like. Therefore, the heat-sensitive adhesive sheet of the present invention and the method for producing an article using the same greatly contribute to the production of resin moldings used for exteriors of home electric appliances, exteriors of mobile terminals, interiors and exteriors of automobiles, and the like. be able to.

FIG. 2 is an image diagram showing an example of a domain with a belt-like structure (lamellar shape). FIG. 2 is an image diagram showing an example of a domain having a belt-like structure (cylindrical shape); FIG. 3 is an image diagram showing an example of a domain with a non-strip structure.

The heat-sensitive adhesive sheet of the present invention has a tensile loss tangent (tan δ) peak temperature measured at a frequency of 3 Hz within the range of -50°C to 200°C of 90°C or more and at least one or more and -20°C or less. A heat-sensitive adhesive layer (a) having at least one or more and having a tensile storage modulus (E′ _a100 ) at 100° C. of 5×10 ⁵ Pa to 1×10 ⁸ Pa, Provided is a heat-sensitive adhesive sheet (A) used for laminating a thermoplastic laminating material (B) as an adhesive layer to the surface of a molding (C).

The heat-sensitive adhesive sheet has the heat-sensitive adhesive layer (a) when the thermoplastic laminating material (B) is heated and laminated to the surface of the molding (C) while being deformed in a three-dimensional direction. The heat-sensitive adhesive sheet (A) can suppress the formation of air bubbles due to gas generation from the thermoplastic bonding material (B) and the peeling of the thermoplastic bonding material (B) due to repulsion from the curved surface, which impairs the appearance. A laminate can be obtained without

Further, according to the heat-sensitive adhesive sheet, the thermoplastic lamination material (B) and the molding (C) are adhered by the heat-sensitive adhesive sheet (A) having the heat-sensitive adhesive layer (a), thereby Even if the composite is left in a hot and humid environment, it suppresses the formation and peeling of bubbles due to gas that can be generated from at least one of the thermoplastic laminating material (B) and the molded product (C), and is left in a cold environment. It is possible to suppress lifting and peeling between the thermoplastic pasting material and the molded product even when the heat is applied or cold and heat are repeated.

Furthermore, the heat-sensitive adhesive sheet of the present invention, in addition to the above-mentioned effects, has a low room-temperature adhesiveness due to the predetermined physical properties, so that it is difficult for dust to adhere to it and can be easily reapplied. In addition, since the heat-sensitive adhesive sheet of the present invention has low room-temperature adhesiveness, it can be suitably used for bonding the molded thermoplastic bonding material (B) and the molding (C). More specifically, the thermoplastic lamination material (B) is preformed to match the shape of the molding (C), and the thermoplastic lamination material (B) after molding and the molding (C) are bonded together as an adhesive sheet. When the adhesive sheet has high room-temperature adhesiveness, the molded thermoplastic lamination material (B) is difficult to fit through the adhesive sheet and may not be sufficiently joined. be. On the other hand, according to the heat-sensitive adhesive sheet of the present invention, since the room-temperature adhesiveness is low, it is possible to sufficiently fit and join the formed members.

The heat-sensitive adhesive layer (a) and the heat-sensitive adhesive sheet (A) are adhered to the thermoplastic lamination material (B) or molded article (C) at a temperature of 23°C and a relative humidity of 50% RH. Immediately after, it is 1 N/cm or less, and by heating at 90° C. to 200° C. for 1 second to 300 seconds, the adhesive strength is defined as changing to 5 N/cm or more at a temperature of 23° C. and a relative humidity of 50% RH. .

As the heat-sensitive adhesive sheet (A), one composed of a single layer or two or more layers of the heat-sensitive adhesive layer (a) can be used.

1. Thermal adhesive sheet (A)
The heat-sensitive adhesive sheet (A) of the present invention has a tensile loss tangent (tan δ) peak temperature of at least 90° C. or higher within the range of −50° C. to 200° C. at a frequency of 3 Hz. Use a heat-sensitive adhesive layer (a) having at least one at least one and at least one at -20°C or less and having a tensile storage elastic modulus (E' _a100 ) at 100°C of 5 × 10 ⁵ Pa to 1 × 10 ⁸ Pa do. By using the heat-sensitive adhesive layer (a) as the adhesive layer of the heat-sensitive adhesive sheet (A), the thermoplastic laminating material (B) is heated to 90 ° C. to 200 ° C. and stuck to the surface of the molded product (C). When combining, the heat-sensitive adhesive layer (a) constituting the heat-sensitive adhesive sheet (A) enables heat-sensitive adhesion, and the formation of bubbles due to gas that can be generated from the thermoplastic lamination material (B) and the thermoplastic It is possible to suppress the peeling of the bonding material (B) due to repulsion from the curved surface, and to obtain a bonded product without impairing the appearance. Furthermore, the heat-sensitive adhesive layer (a) can be used as a thermoplastic laminate (B) or molded article (C) even if the laminate is left in a hot and humid environment, a cold environment, or a cold environment. It is possible to suppress the formation of bubbles due to gas generated from at least one of the above, and to suppress the peeling due to the strain caused by the difference in thermal expansion. Thus, the heat-sensitive adhesive layer (a) serves as an adhesive layer of the heat-sensitive adhesive sheet (A) having both appropriate hardness and adhesive strength.

At least one peak temperature of the loss tangent above 90° C. is preferably in the range of 100° C. to 150° C., more preferably in the range of 110° C. to 140° C., and 110° C. to 130° C. is particularly preferred. Since the peak temperature is within the above temperature range, when the thermoplastic lamination material (B) is heated to a softened state suitable for three-dimensional deformation and lamination, the heat-sensitive adhesive layer (a) is Acquire appropriate flexibility to enable heat-sensitive adhesion, and suppress bubble formation due to gas that can be generated from the thermoplastic bonding material (B) and peeling due to repulsion from the curved surface of the thermoplastic bonding material (B). can be done.

In addition, at least one peak temperature of the loss tangent below -20 ° C. is preferably in the range of -60 ° C. to -20 ° C., more preferably in the range of -50 ° C. to -25 ° C. It is preferably in the range of -40°C to -25°C, particularly preferably. Since there is a peak temperature in the above temperature range, even when the laminated product of the thermoplastic laminated material (B) and the molded product (C) is used in a cold environment or is repeatedly exposed to cold and heat, the heat-sensitive adhesive The layer (a) can maintain appropriate flexibility, and the distortion caused by the difference in thermal expansion between the thermoplastic laminate (B) and the molded product (C) constitutes the heat-sensitive adhesive sheet (A). The heat-sensitive adhesive layer (a) is relaxed, and lifting and peeling between the thermoplastic laminating material (B) and the molding (C) can be suppressed.

The tensile storage modulus (E' _a100 ) at 100° C. is preferably 1×10 ⁶ Pa to 7×10 ⁷ Pa, more preferably 3×10 ⁶ Pa to 5×10 ⁷ Pa, and 3×10 6 Pa to 5×10 7 Pa. It is particularly preferred that the pressure is from ×10 ⁶ Pa to 3×10 ⁷ Pa. By using the heat-sensitive adhesive layer (a) having a tensile storage modulus in the range described above, the thermoplastic laminating material (B) is heated at 90° C. to 200° C. for about 1 second to 300 seconds to form a molded product ( When laminating to C), it becomes a heat-sensitive adhesive layer having both appropriate hardness and adhesiveness, and the formation of bubbles due to gas that can be generated from the thermoplastic laminating material (B) and the thermoplastic laminating material (B) ) can suppress peeling due to curved surface repulsion. Adhesion of the heat-sensitive adhesive sheet (A) having both appropriate hardness and adhesive strength capable of suppressing the formation and peeling of air bubbles even when the laminate is left in a hot and humid environment, a cold environment, or a cold environment. becomes the agent layer.

The loss tangent (tan δ) of the heat-sensitive adhesive layer (a) at a peak temperature of 90 ° C. or higher is preferably 2.0 or less, more preferably 1.5 or less, and the thermoplastic lamination material (B) is appropriately used. When the heat-sensitive adhesive layer (a) is heated to a softened state and laminated, the heat-sensitive adhesive layer (a) obtains appropriate flexibility and adheres heat-sensitively, and bubbles generated by the gas that can be generated from the thermoplastic laminating material (B) are prevented. A range of 0.3 to 1.0 is particularly preferable in terms of suppressing formation and peeling of the thermoplastic lamination material (B) due to repulsion from curved surfaces.

The loss tangent (tan δ) of the heat-sensitive adhesive layer (a) at a peak temperature of −20° C. or lower is preferably 2.0 or less, more preferably 1.5 or less. Even if the laminate adhered with the heat-sensitive adhesive sheet (A) thus constructed is left in a cold environment or in a hot or cold environment, the difference in thermal expansion between the thermoplastic laminate (B) and the molded article (C) The range of 0.3 to 1.0 is particularly preferable in order to maintain appropriate hardness and adhesive strength that can suppress peeling due to generated strain in a low-temperature environment.

The thermal adhesive layer (a) has a tensile storage modulus (E′ _a-20 ) at −20° C. of preferably 5×10 ⁶ Pa to 3×10 ⁹ Pa, more preferably 1×10 ⁷ Pa to 9 × 10 ⁸ Pa is more preferable. The heat-sensitive adhesive layer (a) relieves the strain caused by the difference in thermal expansion between the material (B) and the molded product (C), and the float between the thermoplastic lamination material (B) and the molded product (C). 3×10 ⁷ Pa to 7×10 ⁸ Pa is particularly preferable in terms of suppressing peeling.

The thermal adhesive layer (a) preferably has a tensile storage modulus (E′ _a25 ) at 25° C. of 1×10 ⁶ Pa to 1×10 ⁹ Pa, more preferably 5×10 ⁶ Pa to 7×10 ⁸ . It is more preferably Pa, which facilitates position correction when attaching the thermoplastic bonding material to a pressure molding machine, a vacuum molding machine, a TOM molding machine, etc. at room temperature, and the thermoplastic bonding material (B ) and the molded product (C) is rapidly left in a cold environment from room temperature, or when cold and heat are repeated, the ^float and peeling are suppressed. 10 ⁸ Pa is more preferable.

In addition, the thermal adhesive layer (a) preferably has a tensile storage modulus (E′ _a150 ) at 150° C. of 1×10 ⁵ Pa to 1×10 ⁷ Pa, more preferably 1×10 ⁵ Pa to 7× 10 ⁶ Pa is more preferable, and when the thermoplastic lamination material (B) is heated at 90 ° C. to 200 ° C. for about 1 second to 300 seconds and laminated to the molded product (C), appropriate hardness and adhesiveness In addition to being able to suppress the formation of bubbles due to gas that can be generated from the thermoplastic bonding material (B) and the peeling of the thermoplastic bonding material (B) due to curved surface repulsion, 1×10 ⁵ Pa to 5×10 ⁶ Pa is particularly preferred.

The tensile storage elastic modulus and loss tangent (tan δ) were measured using a viscoelasticity tester (manufactured by TA Instruments Japan, trade name: RSA III) in a tensile mode at a frequency of 3.5. The tensile storage modulus (E′) and loss tangent (tan δ) are measured in the temperature range from −50° C. to 200° C. under conditions of 0 Hz and a heating rate of 5° C./min. The test piece used in the above measurement was obtained by laminating the heat-sensitive adhesive layer (a) to a thickness of 400 μm to 600 μm, setting the width to 5 mm and the length of the measurement part to 20 mm, and adjusting the length of the handle at each end. A rectangular piece cut to 20 mm is used.

[Heat-sensitive adhesive layer (a)]
The heat-sensitive adhesive layer (a) is formed of an adhesive composition. For example, the surface of a release liner or the like is coated with an adhesive composition solution obtained by dissolving the adhesive composition described later in an organic solvent or the like, and dried. can be manufactured by equating

The adhesive composition is not particularly limited as long as it can have the physical properties described above. An adhesive composition containing a block copolymer having a polymer block (S2) having a transition temperature can be preferably used. More specifically, a (meth)acrylic triblock copolymer or a vinyl aromatic triblock copolymer (an aromatic vinyl monomer and a conjugated diene monomer) represented by the formula: S2-S1-S2 a triblock copolymer such as a triblock copolymer consisting of a solid), or a (meth)acrylic diblock copolymer or a vinyl aromatic diblock copolymer (aromatic An adhesive composition containing a diblock copolymer such as a diblock copolymer consisting of a group vinyl monomer and a conjugated diene monomer can be used. Among them, it is preferable to use an adhesive composition containing a triblock copolymer represented by the formula: S2-S1-S2 in order to suppress bubble formation and peeling.

By using said block copolymer, polymer blocks (S1) and polymer blocks (S2) form domains. By forming the domains, the heat-sensitive adhesive sheet (A) is used as an adhesive layer, and the thermoplastic laminating material (B) is heated and laminated to the surface of the molding (C) while being deformed in a three-dimensional direction. At this time, the domain of the polymer block (S2) having a glass transition temperature of 90° C. or higher contained in the heat-sensitive adhesive layer (a) is prevented from forming air bubbles by the gas that can be generated from the thermoplastic laminating material (B). and suppresses peeling due to curved surface repulsion of the thermoplastic lamination material (B), and even if the lamination material is left in a hot and humid environment, at least one of the thermoplastic lamination material (B) or the molded article (C) Suppresses bubble formation and peeling caused by gas that may occur. On the other hand, the domain of the polymer block (S1) having a glass transition temperature of −20° C. or lower contained in the heat-sensitive adhesive layer (a) is 90° C. to 200° C. in the thermoplastic laminating material (B). Heating for about 1 second to 300 seconds to improve the heat-sensitive adhesiveness when laminating to the molded product (C), and when the laminated product is used in a cold environment or when cold and heat are repeated , Alleviating strain due to the difference in thermal expansion between the thermoplastic bonding material (B) and the molded product (C), and suppressing lifting and peeling between the thermoplastic bonding material (B) and the molded product (C) .

The glass transition temperatures of the polymer block (S1) and the polymer block (S2) of the block copolymer are determined in a curve obtained by analyzing the copolymer resin with a differential scanning calorimeter (DSC). S1) and the extrapolated start temperature of the transition region of the polymer block (S2).

When the (meth)acrylic block copolymer is used as the copolymer contained in the adhesive composition, the polymer block (S2 ) includes, for example, polymer blocks composed of methacrylic acid esters such as methyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate and phenyl methacrylate; and acrylic acid esters such as isobornyl acrylate. These may be used alone, or two or more of them may be used in combination to form the polymer block (S2). Among these, it is easy to adjust the viscoelasticity within the predetermined range, suppresses the formation of air bubbles and peeling of the thermoplastic laminating material (B) due to repulsion from the curved surface, and prevents the lamination from being left in a hot and humid environment. It is more preferable to form the polymer block (S2) using methyl methacrylate because it is easy to suppress the formation and peeling of air bubbles and the heat-sensitive adhesive layer (a) has excellent moldability and heat-sensitive adhesiveness. preferable.

Examples of the polymer block (S1) having a glass transition temperature of −20° C. or higher, which constitutes the (meth)acrylic block copolymer, include n-lauryl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, and methacrylic acid. Stearyl, methacrylic acid esters such as 2-ethoxyethyl methacrylate; ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, amyl acrylate, acrylic acid Examples include polymer blocks such as isoamyl, n-hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, 2-methoxyethyl acrylate, and other acrylate esters. These may be used alone, or two or more of them may be used in combination to form the polymer block (S1). Among these, it is easy to adjust the viscoelasticity within the predetermined range, and it is easy to relax the strain due to the difference in thermal expansion when the laminated product is used in a cold environment or when cold and heat are repeated, and heat sensitivity. The polymer block (S1) is formed using any one of ethyl acrylate, isopropyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, since the adhesive layer (a) has excellent heat-sensitive adhesive properties. is preferred.

The method for obtaining the glass transition point may be obtained by any method, and a measurement method based on the plastic transition temperature measurement method (JIS K7121-1987) using differential thermal analysis or differential scanning calorimetry is used. is preferred.

The glass transition temperature of the polymer block (S2) is preferably in the range of 90°C to 150°C, more preferably 100°C to 130°C. Suppresses peeling of the thermoplastic lamination material (B) due to curved surface repulsion, and even if the lamination material is left in a hot and humid environment, it is generated from at least one of the thermoplastic lamination material (B) and the molded article (C). A temperature of 100° C. to 120° C. is most preferable in order to suppress the formation and peeling of air bubbles caused by possible gases.

The glass transition temperature of the polymer block (S1) is preferably in the range of -90°C to -20°C, more preferably -70°C to -30°C. Heating at 200 ° C. for about 1 second to 300 seconds increases the heat-sensitive adhesiveness when laminating to the molded product (C), and when the laminated product is used in a cold environment or when cold and heat are repeated. For this, the strain due to the difference in thermal expansion between the thermoplastic bonding material (B) and the molded product (C) is relaxed, and the separation and peeling between the thermoplastic bonding material (B) and the molded product (C) are prevented. A temperature of -60°C to -40°C is most preferable for suppression.

The (meth)acrylic block copolymer may have other polymer blocks in addition to the polymer blocks (S1) and (S2). Other polymer blocks include, for example, methacrylic acid, acrylic acid, methacrylonitrile, acrylonitrile, vinyl acetate, styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, ethylene, propylene, butadiene, isobutene, isoprene. , octene, maleic anhydride, vinyl chloride, vinylidene chloride, etc., polymer blocks or hydrogenated products thereof; polyethylene terephthalate, polybutylene terephthalate, polylactic acid, polyurethane, polydimethylsiloxane Combined blocks and the like are included. These may be used alone, or two or more of them may be used in combination to form a polymer block. When the heat-sensitive adhesive layer (a) is in contact with a decorative layer formed by vapor deposition of metal or a functional layer with metal wiring, etc., an acid group such as methacrylic acid or acrylic acid is added in order to prevent corrosion or discoloration of the metal layer. It is preferable that the (meth)acrylic block copolymer does not contain a polymer block composed of the containing monomer.

The (meth)acrylic block copolymer has a crosslinkable functional group and may be crosslinked with a crosslinking agent in order to improve cohesion. Examples of crosslinkable functional groups include hydroxyl groups, carboxyl groups, glycidyl groups, and the like. If a hydroxyl group is present, a cross-linking agent such as a polyfunctional isocyanate compound is used. If a carboxyl group is present, a cross-linking agent such as a polyfunctional epoxy compound is used. When it has, a cross-linking agent such as an amine-based compound, an acid anhydride, or a polyfunctional thiol can be used. The content of the crosslinkable functional group is preferably 1,000 equivalents to 100,000 equivalents, and is preferably 3,000 equivalents to 50,000 equivalents, and preferably 5,000 equivalents to 20,000 equivalent weight is particularly preferred. When the heat-sensitive adhesive layer (a) is in contact with a decorative layer deposited by metal deposition or a functional layer with metal wiring, etc., in order to prevent corrosion and discoloration of the metal layer, a hydroxyl group is included as a crosslinkable functional group. and cross-linking with a polyfunctional isocyanate compound or the like.

When a vinyl aromatic block copolymer composed of the aromatic vinyl monomer and the conjugated diene monomer is used as the copolymer contained in the adhesive composition, the glass transition temperature is 90° C. or higher. Polymer blocks (S2) having temperature include polymer blocks composed of aromatic vinyl monomer units, such as polymers composed of styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, etc. block. These may be used alone or in combination of two or more. Among these, it is easy to adjust the viscoelasticity within the predetermined range, suppresses the formation of air bubbles and peeling of the thermoplastic laminating material (B) due to repulsion from the curved surface, and prevents the lamination from being left in a hot and humid environment. It is preferable to use styrene to form the polymer block (S2) because the formation and peeling of the heat-sensitive adhesive layer (a) are easily suppressed and the heat-sensitive adhesive layer (a) has excellent moldability and heat-sensitive adhesive properties.

As the polymer block (S1) having a glass transition temperature of −20° C. or lower, which constitutes the vinyl aromatic block copolymer composed of the aromatic vinyl monomer and the conjugated diene monomer, a conjugated diene monomer Examples include polymer blocks composed of monounits, such as unsaturated hydrocarbons such as butadiene, isobutene and isoprene, and hydrogenated products thereof. It is easy to adjust the viscoelasticity within the predetermined range, and it is easy to relax the distortion due to the difference in thermal expansion when the laminated product is used in a cold environment or is repeatedly subjected to cold and heat, and the heat-sensitive adhesive layer ( The polymer block (S1) is formed by using any hydrogenated unsaturated hydrocarbon selected from the group consisting of butadiene, isobutene and isoprene because of its excellent heat-sensitive adhesiveness and deterioration resistance of a). preferably.

Although the weight average molecular weight of the block copolymer is not particularly limited, it is preferably in the range of 10,000 to 500,000, more preferably in the range of 50,000 to 200,000. ) is particularly preferably 70,000 to 120,000 in order to obtain transparency and moldability. When the thermoplastic lamination material (B) is heated and laminated to the molding (C), the heat-sensitive adhesive layer (a) obtains appropriate flexibility and heat-sensitive adhesiveness. and facilitates the formation of domains of the polymer block (S1) and the polymer block (S2), and the formation of bubbles due to gas that can be generated from the thermoplastic bonding material (B) and the thermoplastic bonding material (B) air bubbles that can be generated from at least one of the thermoplastic lamination material (B) and the molded article (C) even if the lamination is left in a hot and humid environment. formation and peeling can be suppressed. Furthermore, when the laminated product is used in a cold environment or is repeatedly exposed to cold and heat, the distortion caused by the difference in thermal expansion between the thermoplastic laminated material (B) and the molded product (C) is alleviated, Lifting and peeling between the plastic bonding material (B) and the molding (C) can be suppressed. In addition, the said weight average molecular weight shows the value measured on the following conditions by the gel permeation chromatography (GPC) method.

Measuring device: high-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series and used.
"TSKgel G5000" (7.8mm I.D. x 30cm) x 1 "TSKgel G4000" (7.8mm I.D. x 30cm) x 1 "TSKgel G3000" (7.8mm I.D. x 30cm) x 1 Book "TSKgel G2000" (7.8 mm ID x 30 cm) x 1 Detector: RI (differential refractometer)
Column temperature: 40°C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL/min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
Standard sample: A calibration curve was created using the following standard polystyrene.

(standard polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation
The weight-average molecular weight is a value calculated as a conversion value using standard polystyrene for preparation of a calibration curve by gel permeation chromatography (hereinafter referred to as "GPC") analysis.

The content of the polymer block (S2) having a glass transition temperature of 90° C. or higher in the block copolymer is preferably 29% by mass to 49% by mass, more preferably 33% by mass to 46% by mass, and 36% by mass. % to 42% by weight is particularly preferred. When the polymer block (S2) is less than 29% by mass, the heat-sensitive adhesive layer (a) is softened when the thermoplastic laminating material (B) is heated and laminated to the molding (C). Therefore, the formation of bubbles due to the gas that can be generated from the thermoplastic bonding material (B) and the peeling due to the repulsion of the curved surface of the thermoplastic bonding material (B) are likely to occur, and the bonded material is exposed to a hot and humid environment. Gases that can be generated from at least one of the thermoplastic laminating material (B) and the molding (C) when left unattended are likely to cause bubble formation and peeling. Further, when the polymer block (S2) is more than 49% by mass, the heat-sensitive adhesiveness of the heat-sensitive adhesive layer (a) is insufficient, and the laminated product is used in a cold environment, and cold heat is applied. When repeated, the strain due to the difference in thermal expansion between the thermoplastic bonding material (B) and the molded product (C) cannot be relaxed, and the distortion between the thermoplastic bonding material (B) and the molded product (C) cannot be relieved. Floating and peeling are likely to occur.

The content of the polymer block (S1) having a glass transition temperature of −20° C. or lower in the block copolymer is preferably 51% by mass to 71% by mass, more preferably 54% by mass to 67% by mass. % to 64% by weight is particularly preferred. When the polymer block (S1) is less than 51% by mass, the heat-sensitive adhesive layer (a) is softened when the thermoplastic laminating material (B) is heated and laminated to the molding (C). insufficient, the heat-sensitive adhesiveness of the heat-sensitive adhesive layer (a) is insufficient, and when the laminate is used in a cold environment or subjected to repeated cold and heat, the thermoplastic laminate (B) Distortion due to the difference in thermal expansion with the molding (C) cannot be relaxed, and the thermoplastic bonding material (B) and the molding (C) are likely to separate or separate. Further, when the polymer block (S1) is more than 71% by mass, formation of bubbles due to gas that can be generated from the thermoplastic bonding material (B) and peeling due to repulsion from the curved surface of the thermoplastic bonding material (B) is likely to occur, and when the laminated product is left in a hot and humid environment, the formation and peeling of bubbles due to gas that can be generated from at least one of the thermoplastic laminated material (B) and the molded product (C). more likely to occur.

The block copolymer contained in the adhesive composition may be one type of block copolymer, or a mixture of two or more types of block copolymers having different polymer block contents. good too. The content of the polymer block (S1) or (S2) when two or more block copolymers are contained is the content of the polymer block (S1) or (S2) in each block copolymer. is the average value of, for example, the content of the polymer block (S1) or (S2) in the two block copolymer mixtures of the block copolymer (F) and the block copolymer (G) is the block copolymer It is calculated by the following formula (1) from the content of the polymer block (S1) or (S2) in each of the block copolymers of the polymers (F) and (G).

Content rate [% by mass] of polymer block (S1) or (S2) in block copolymer mixture = [content rate [% by mass] of polymer block (S1) or (S2) in block copolymer (F) ] x content of block copolymer (F) in mixture of block copolymers [% by mass]/100] + [content of polymer block (S1) or (S2) in block copolymer (G) rate [% by mass] x content of block copolymer (G) in mixture of block copolymers [% by mass]/100] Formula (1)

When two or more types of the block copolymers are contained in the adhesive composition, the absolute value of the content ratio difference of the polymer blocks (S1) and (S2) between the block copolymers indicates the formation of domains. In order to facilitate the transparency of the heat-sensitive adhesive layer (a), the content is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less.

The size of the domain of the polymer block (S2) of the block copolymer contained in the adhesive composition formed on the surface or inside of the heat-sensitive adhesive layer (a) is determined by the thermoplastic bonding material (B ), suppressing the formation of bubbles due to gas generated from the thermoplastic lamination material (B) and the peeling of the thermoplastic lamination material (B) due to the curved surface repulsion, and even if the lamination material is left in a hot and humid environment, the thermoplastic lamination material (B ) or suppress the formation and peeling of bubbles due to gas that can be generated from at least one of the molded product (C), or when used in a cold environment or when cold and heat are repeated, the thermoplastic laminate (B) In order to suppress lifting and peeling due to distortion due to a difference in thermal expansion from the molded product (C), it is preferable to form relatively large domains, and the length of the long side of the domain of the polymer block (S2) is 160 nm or more on average. More preferably, it has a strip-like structure such as a cylinder or a lamellar shape with an average long side length of 160 nm or more. (eg Figures 1 and 2). The size of the domain is arbitrary for an image of a separated phase obtained by scanning the surface or cross section of the heat-sensitive adhesive layer (a) in the phase mode of a scanning probe microscope (SPM) in a field of view of 1 μm. is the average value obtained by measuring the length of the long side of the polymer block (S2) of the domain of 5 or more points. "Nano-DST" manufactured by Pacific Nanotechnology is used as a scanning probe microscope, and the measurement can be performed in a close contact mode. When the adhesive composition is formed of a mixture of two or more block copolymers, the domain size of the polymer block (S2) of the block copolymer contained in the adhesive composition is It refers to the size of a domain formed by aggregation of the polymer blocks (S2) of each block copolymer forming the mixture. For example, the adhesive composition includes a block copolymer X having a polymer block (S1x) and a polymer block (S2x), and a block copolymer Y having a polymer block (S1y) and a polymer block (S2y). , the polymer block (S2x) of the block copolymer X and the polymer block (S2y) of the block copolymer X aggregate on the surface or inside the heat-sensitive adhesive layer (a) Since one type of polymer block (S2) domain is formed, the length of the long side of the one type of domain is measured.

The method for producing the block copolymer is not particularly limited, and examples thereof include living anionic polymerization disclosed in JP-A-04-246488 and JP-A-2014-084334.

The block copolymer may be produced in the presence of an organic solvent.

Examples of the organic solvent include ester solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, and cyclohexanone; and ether esters such as methyl cellosolve acetate and butyl cellosolve acetate. A system solvent, an aromatic hydrocarbon solvent such as toluene and xylene, an amide solvent such as dimethylformamide and dimethylacetamide, and the like can be used alone or in combination of two or more.

The adhesive composition may contain other additives as necessary.

Examples of other additives include silane coupling agents, antioxidants, light stabilizers, rust inhibitors, thixotropic agents, leveling agents, tackifiers, antistatic agents, flame retardants, coloring dyes, and coloring agents. A pigment or the like can be used. These additives may be used alone or in combination of two or more. Among these, when the laminated product manufactured by the method of the present invention is used in applications where it is exposed to the outdoors or left in a hot and humid environment, high light resistance and yellowing resistance are required. It is preferable to contain stabilizers, antioxidants, and the like. Moreover, it is preferable to contain a tackifier or the like in order to further improve the heat-sensitive adhesiveness.

The light stabilizer captures radicals generated by photodegradation. For example, radical scavengers such as thiol compounds, thioether compounds and hindered amine compounds; UV absorbers such as benzophenone compounds and benzoate compounds can be used. can. These light stabilizers may be used alone or in combination of two or more. Among these, hindered amine compounds are preferably used because they can further improve yellowing resistance.

When the light stabilizer is used, the amount used is 0.00 parts per 100 parts by mass of the total amount of the one or more block copolymers, from the viewpoint of further improving light resistance and yellowing resistance. It is preferably in the range of 01 parts by mass to 10 parts by mass, and more preferably in the range of 0.05 parts by mass to 3 parts by mass so as not to impair the heat-sensitive adhesive properties.

The antioxidants include hindered phenol compounds (primary antioxidants) that capture radicals generated by thermal deterioration, and phosphorus compounds and sulfur compounds (secondary antioxidants) that decompose peroxides generated by thermal deterioration. agent) etc. can be used.

Among these, it is preferable to use a phosphorus compound in order to further improve the antioxidant property, and triphenylphosphine, bis(2,4-di-tert-butyl-6-methylphenyl)=ethyl=phosphite and It is more preferable to use one or more antioxidants selected from the group consisting of tris(2,4-di-tert-butylphenyl)phosphite, triphenylphosphine, bis(2,4-di-tert-butyl -6-methylphenyl)=ethyl=phosphite is more preferably used.

When the antioxidant is used, the amount used is 0.01 part by mass with respect to 100 parts by mass of the total amount of the one or more block copolymers from the viewpoint of further improving the antioxidant property. It is preferably in the range of up to 10 parts by mass, and more preferably in the range of 0.05 parts by mass to 3 parts by mass so as not to impair the heat-sensitive adhesive properties.

As the tackifier, any tackifier resin such as styrene resin, rosin resin, terpene resin, and aliphatic hydrocarbon resin can be used, and the viscoelasticity is easily adjusted within the predetermined range. It is preferable to use rosin-based resins and terpene-based resins, and hydrogenated rosin-based resins and terpene-based resins are more preferable because they are excellent in light resistance and yellowing resistance. Use is particularly preferred.

When the tackifier is used, the amount used is 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the total amount of the one or more block copolymers, from the viewpoint of further improving the heat-sensitive adhesiveness. It is preferably in the range of 5 parts by mass to 20 parts by mass, and more preferably in the range of 5 parts by mass to 20 parts by mass without impairing the suppression of air bubble formation when heated.

In addition, for the purpose of suppressing repelling when the heat-sensitive adhesive layer (a) is applied on the release liner, and improving handling workability such as the cutting process of the heat-sensitive adhesive sheet (A) and the peeling process of the release liner, etc., a transparent Any thermoplastic resin may be used in combination with the components described above as long as the properties are not impaired. Examples of the thermoplastic resin include urethane-based resins, acrylic-based resins, polyester-based resins, and epoxy-based resins. It is more preferable to use a thermoplastic resin that can be crosslinked by.

The thermoplastic resin is preferably semi-solid or solid at 25° C., and has a weight average molecular weight preferably in the range of 5,000 to 200,000, more preferably in the range of 15,000 to 100,000. is more preferred. The weight average molecular weight of the thermoplastic resin indicates a value obtained by measuring in the same manner as the weight average molecular weight of the block copolymer.

The amount of the thermoplastic resin used is preferably 1 part by mass to 50 parts by mass, preferably 3 parts by mass to 20 parts by mass, based on the total amount of 100 parts by mass of the one or more block copolymers. This is particularly preferable in that the cohesive force of the block copolymer contained in the heat-sensitive adhesive layer (a) is not lowered, and the formation of air bubbles, floating, and peeling when heated are suppressed.

The purpose of adjusting the dielectric loss tangent and the dielectric constant of the heat-sensitive adhesive layer (a) is to read electric signals by passing high-frequency electric pulses in the vicinity of the laminated material laminated by the method of the present invention. In addition, a polyolefin resin, an inorganic filler, or the like may be added as long as the transparency is not impaired.

The polyolefin resin is preferably an olefin resin such as polyethylene resin or polypropylene resin having a dielectric constant of about 2 to 3, or a rubber resin such as isoprene resin or butadiene resin. For the purpose of improving the compatibility of , some of the side chains may be chlorinated or modified with a carboxylic acid to partially improve the polarity.

As the inorganic filler, it is preferable to use an inorganic filler having a dielectric loss tangent of about 10 ⁻⁴ to 10 ⁻⁵ such as boron nitride, forteslite, cordierite, silica, magnesium oxide, and alumina. It is more preferable to use silica, which has excellent compatibility with adhesive compositions such as silica, and can enhance the transparency of the heat-sensitive adhesive layer (a).

As the inorganic filler, any shape such as spherical or pulverized can be used. In order to improve compatibility with the adhesive composition such as the block copolymer, titanate coupling or aluminum filler is added to the surface. Surface-treated materials such as nate coupling and silane coupling may be used.

As for the particle size of the inorganic filler, it is preferable to use one having a cumulative under-sieve distribution 50% particle size of 10 nm to less than 50 μm, more preferably 10 nm to 20 μm, and 1 μm to 10 μm. It is particularly preferable to use one in order to increase the transparency of the adhesive layer (a) and achieve both good dispersibility of the inorganic filler and ease of coating. The cumulative under-sieve distribution 50% particle size of the inorganic filler is measured using a laser diffraction particle size distribution analyzer SALD-3100 manufactured by Shimadzu Corporation using isopropanol as a dispersion medium. can be done.

The amount of the polyolefin resin and the inorganic filler used is 1 part by mass to 50 parts by mass of the total amount of the polyolefin resin and the amount of the inorganic filler with respect to the total amount of 100 parts by mass of the one or more block copolymers. It is preferable to use 5 parts by mass to 20 parts by mass in order to reduce the dielectric loss tangent and the dielectric constant of the adhesive sheet and to suppress the deterioration of the adhesiveness of the heat-sensitive adhesive layer (a). more preferred.

[Heat-sensitive adhesive sheet (A)]
The heat-sensitive adhesive sheet (A) used in the method of the present invention is prepared by, for example, coating the surface of a release liner with a solution of an adhesive composition obtained by dissolving the adhesive composition in an organic solvent or the like, and drying if necessary. It can be manufactured by forming a heat-sensitive adhesive layer (a).

Examples of the organic solvent include ester solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, and cyclohexanone; and ether esters such as methyl cellosolve acetate and butyl cellosolve acetate. A system solvent, an aromatic hydrocarbon solvent such as toluene and xylene, an amide solvent such as dimethylformamide and dimethylacetamide, and the like can be used alone or in combination of two or more.

Examples of the method for applying the solution of the adhesive composition to the surface of the release liner include a method using a comma coater, a lip coater, or the like. The drying can be performed, for example, using a dryer or the like set at a temperature of about 80.degree. C. to 120.degree.

Examples of the release liner include paper such as kraft paper, glassine paper, and fine paper; resin films such as polyethylene, biaxially oriented polypropylene, extruded polypropylene, and polyethylene terephthalate; laminated paper obtained by laminating the paper and resin film; It is possible to use the above-mentioned paper which has been subjected to filling treatment with clay, polyvinyl alcohol, or the like, and which has been subjected to peeling treatment such as a silicone-based compound on one or both sides thereof. In order to increase the transparency of the heat-sensitive adhesive sheet (A), it is preferable to use a release liner obtained by subjecting a resin film to release treatment.

Examples of the release agent for the release liner include silicone-based release agents, aminoalkyd-based release agents, silicone-modified aminoalkyd-based release agents, long-chain alkyl-based release agents, fluorine-based release agents, and the like.

The thickness of the release liner is preferably 38 μm to 150 μm, more preferably 50 μm to 100 μm. By setting the thickness to the above range, the smoothness of the surface of the heat-sensitive adhesive layer (a) after drying is enhanced, the release liner is less likely to stretch during the drying process, and curling after winding into a roll is prevented. can be done.

As the release liner, the heat-sensitive adhesive sheet (A) is heated to 90° C. to 200° C. while the release liner is laminated on one side, and the heat-sensitive adhesive of the heat-sensitive adhesive sheet (A) is heated first. The surface side of the layer (a) and the molded article (C) are pressed and laminated, and after peeling and removing the release liner, only the thermoplastic lamination material (B) is heated to 90°C to 200°C. , When the laminated product is produced through the step of pressing and laminating the thermoplastic laminating material (B) and the heat-sensitive adhesive layer (a), polyethylene, biaxially oriented polypropylene, extruded polypropylene, etc. It is more preferable to use a release liner based on a thermoplastic resin which has a low softening temperature and is easily stretched by heating.

The heat-sensitive adhesive sheet (A) may be sandwiched by any other release liner until it is used in the lamination step. In order to prevent the adhesive sheet from tearing apart when the release liner is peeled off again after being sandwiched, it is preferable to use a release liner having different peel strengths on both sides. Since the heat-sensitive adhesive layer (a) has poor pressure-sensitive adhesiveness at room temperature, when the heat-sensitive adhesive sheet (A) is wound into a roll, it tends to float. It is preferable to use a release liner coated with a silicone-based release agent or a non-silicone-based release agent such as an aminoalkyd release agent, a silicone-modified aminoalkyd resin, or a long-chain alkyl resin.

The thickness of the heat-sensitive adhesive layer (a) is preferably 10 μm to 300 μm, more preferably 25 μm to 250 μm, and more preferably 50 μm to 200 μm. It is particularly preferred to use a thin one. In order to form the above thickness, two or more heat-sensitive adhesive layers (a) may be laminated instead of using a single heat-sensitive adhesive layer (a). When two or more heat-sensitive adhesive layers (a) are laminated, two or more heat-sensitive adhesive layers (a) having different compositions may be laminated as long as the viscoelasticity within the predetermined range is satisfied.

When two or more of the heat-sensitive adhesive layers (a) are laminated, the adhesiveness is poor at room temperature. A method of heat-pressing while passing through a gap between rotating rubber rollers or metal rollers, or a method of temporarily laminating the adhesive surfaces of the heat-sensitive adhesive layer (a) laminated on the release liner at room temperature so as not to introduce air bubbles. Then, it is preferable to use a method of laminating two or more heat-sensitive adhesive layers (a) by heating and curing in an atmosphere of 50° C. or more for 24 hours or more.

Also, the heat-sensitive adhesive sheet (A) may have a structure in which the heat-sensitive adhesive layer (a) is laminated on both sides of a substrate. By inserting the base material into the heat-sensitive adhesive layer (a), the handleability of the heat-sensitive adhesive sheet (A) is improved, and the heat-sensitive adhesive layer (a) is less likely to protrude or be damaged during cutting. Preferred for obtaining excellent dimensional stability.

As the base material, any film or mesh material such as polyethylene terephthalate, polybutylene terephthalate, polyimide, polyphenylene sulfide, polyphenylene ether, polypropylene, polyethylene, and polystyrene can be used. The use of superior polyethylene terephthalate, polypropylene, polyethylene, polystyrene is particularly preferred. The substrate preferably has a thickness of about 1/2 or less of the total thickness of the heat-sensitive adhesive sheet (A), and a thickness of 1 μm to 50 μm is used. It is preferable to use one having a thickness of 2 μm to 25 μm.

When the heat-sensitive adhesive layer (a) is laminated on the base material, the composition of the heat-sensitive adhesive layer (a) is applied to the surface of the base material, or the adhesiveness is poor at room temperature. The heat-sensitive adhesive layer (a) laminated on the release liner is heat-pressed onto the substrate surface by a method such as heat-pressing while passing through a gap between rotating rubber rollers or metal rollers heated to 90 ° C. or higher. Preferably, a) is laminated.

The heat-sensitive adhesive sheet (A) preferably has a thickness of 10 μm to 300 μm, more preferably 25 μm to 250 μm, and more preferably 50 μm to 200 μm. It is particularly preferred to use The heat-sensitive adhesive sheet (A) having a thickness within the above range has excellent heat-sensitive adhesiveness, and the formation of bubbles due to gas that can be generated from the thermoplastic lamination material (B) during heat lamination and the thermoplastic lamination. It is possible to suppress the peeling of the composite material (B) due to the repulsive force of the curved surface, and the gas that can be generated from at least one of the thermoplastic bonding material (B) and the molded product (C) even in a hot and humid environment without going through the curing process. It is possible to suppress the formation and peeling of air bubbles due to The above thickness refers to the thickness not including the release liner.

The heat-sensitive adhesive sheet (A) having the heat-sensitive adhesive layer (a) has excellent heat-sensitive adhesiveness. When heating to 90 ° C. to 200 ° C. and bonding to the surface of the molded product (C), the heat-sensitive adhesive layer (a) constituting the heat-sensitive adhesive sheet (A) separates from the thermoplastic bonding material (B) It is possible to obtain a laminated product without impairing the appearance by suppressing the formation of air bubbles due to gas that may be generated and the peeling of the thermoplastic laminated material (B) due to repulsion from the curved surface. Furthermore, the laminated product bonded with the heat-sensitive adhesive sheet (A) formed on the heat-sensitive adhesive layer (a) is thermoplastic even if left in a hot and humid environment, a cold environment, or a cold environment. It is possible to suppress the formation of bubbles due to gas generated from at least one of the bonding material (B) and the molded product (C), and to suppress peeling due to distortion caused by a difference in thermal expansion.

The heat-sensitive adhesive sheet (A) is preferably transparent and has a light transmittance of 80% or more at a wavelength of 380 nm to 780 nm and a haze of 5.0 or less when the release liner is removed from both sides. It is preferable to use a light transmittance of 85% or more at a wavelength of 380 nm to 780 nm and a haze of 2.0 or less, and a light transmittance of 90% or more at a wavelength of 380 nm to 780 nm. It is particularly preferable to use one with a haze of 1.0 or less. By setting it as the said range, designability can be improved, without impairing the external appearance of the said laminated article. The heat-sensitive adhesive sheet (A) preferably maintains the light transmittance and haze even after being left in a hot and humid environment.

The heat-sensitive adhesive sheet (A) is heat-sensitive adhesive, and preferably has a 180° peeling adhesive strength of 1 N/cm or less immediately after application under an environment of a temperature of 23° C. and a relative humidity of 50% RH. It is more preferably 7 N/cm or less, and particularly preferably 0.1 N/cm to 0.5 N/cm. By setting the above range, the thermoplastic laminating material (B) laminated with the heat-sensitive adhesive sheet (A) or the heat-sensitive adhesive sheet (A) laminated on the release liner can be processed by a pressure molding machine, a vacuum molding machine, or a TOM molding machine. When attached to a lamination apparatus such as a lamination device, the position can be easily corrected, and dirt and dust do not adhere to the surface of the adhesive layer, so that the appearance after lamination is not impaired. Also, when the thermoplastic pasting material is first formed along the shape of the molded article and then laminated to the surface of the molded article with the liquid adhesive or adhesive sheet, the bonding position may be shifted. However, since it is easily peeled off, it is easy to correct the misaligned position, and air bubbles are less likely to be involved in the interface between the heat-sensitive adhesive layer (a) and the molding (C).

The 180° peeling adhesive strength of the heat-sensitive adhesive sheet (A) after heat application is 5 N/cm or more in an environment of temperature 23°C and relative humidity 50% RH and in an environment of temperature 90°C. It is preferably 8 N/cm to 50 N/cm, and particularly preferably 10 N/cm to 30 N/cm. By setting it to the above range, when the heat-sensitive adhesive sheet (A) is used as an adhesive layer and the thermoplastic lamination material (B) is heated to 90 ° C. to 200 ° C. and laminated to the surface of the molded product (C). , By the heat-sensitive adhesive layer (a) constituting the heat-sensitive adhesive sheet (A), the formation of bubbles due to gas that can be generated from the thermoplastic lamination material (B) and the repulsion of the curved surface of the thermoplastic lamination material (B) Peeling can be suppressed. Furthermore, even if the laminate adhered with the heat-sensitive adhesive sheet (A) formed on the heat-sensitive adhesive layer (a) is left in a hot and humid environment, the thermoplastic laminate (B) or the molded product can be used. It is possible to suppress the peeling due to the formation of bubbles due to the gas that can be generated from at least one of the objects (C).

The 180° peeling adhesive strength of the heat-sensitive adhesive sheet (A) after heat application is preferably 1 N/cm or more, more preferably 2 N/cm to 30 N/cm, in an environment of -20°C. Preferably, 3 N/cm to 20 N/cm are particularly preferred. By setting the above range, even when the laminated product is left in a cold environment or a cold environment, heat due to strain generated from the difference in thermal expansion between the thermoplastic laminated material (B) and the molded product (C) Lifting and peeling between the plastic bonding material (B) and the molding (C) can be suppressed.

In addition, the 180° peeling adhesive strength immediately after application under an environment of a temperature of 23°C and a relative humidity of 50% RH was 120 after removing the release liner on one side of the heat-sensitive adhesive sheet (A) having release liners laminated on both sides. After laminating a 125 μm thick polycarbonate sheet (manufactured by Teijin Limited, “Panlite PC-2151”) with a thermal laminator heated to ° C., it was cut to a width of 1 cm and placed at 23 ° C. and 50% RH. Placed on a polycarbonate plate with a smooth surface of about 1 mm to 3 mm, and applied pressure to one reciprocation at a speed of 300 mm / min with a 2 kg roller as a sample, Tensilon type tensile tester equipped with a constant temperature bath (A Co., Ltd. And D, "RTG-1210"), in an atmosphere of 23 ° C. and 50% RH, within 1 minute after pressurization, the polycarbonate sheet was started to be pulled in the direction of 180 ° at a speed of 50 mm / min. It is obtained by measuring the actual peeling resistance.
The 180° peeling adhesive strength after heat application was measured at 140°C for 15 seconds using a heat press (manufactured by Tester Sangyo Co., Ltd., "TP-750 Air Press") instead of applying one reciprocating pressure with the 2 kg roller. A sample was prepared by heating and pressurizing at a pressure of 0.2 MPa, and in the same manner as above, in an atmosphere of -20 ° C., in an atmosphere of 23 ° C. and a relative humidity of 50% RH, and in an atmosphere of 90 ° C. It is obtained by measuring the peel resistance when the polycarbonate sheet is pulled in the 180° direction at a rate of 50 mm/min.
Humidity is not controlled when measuring at temperatures of -20°C and 90°C.

2. Method for producing an article In the method for producing an article of the present invention, the thermoplastic lamination material (B) is laminated on the surface of the molded article (C) using the heat-sensitive adhesive layer (a) of the above-described heat-sensitive adhesive sheet as an adhesive layer. A method for manufacturing an article.

[Thermoplastic laminating material (B)]
Examples of the thermoplastic bonding material (B) to be bonded by the method of the present invention include transparent members made of plastic.

Examples of the thermoplastic laminating material (B) include any resin base materials, such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyral. rate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone, polyethersulfone, polyetherimide, polyimide, nylon, (meth ) Resin substrates such as acrylic resins and alloys thereof can be used. Among them, polycarbonates, (meth)acrylic resins, and alloys thereof are preferable as the resin base material in order to achieve both high transparency and surface hardness. However, resin substrates such as polycarbonates, (meth)acrylic resins, and alloys thereof tend to instantly generate gas when heated to about 85° C. or higher, which causes the formation of air bubbles. With the lamination method of the present invention using the heat-sensitive adhesive sheet (A), even when the resin base material is used, air bubbles are unlikely to be formed due to the generation of the gas, and the appearance is not impaired. It is possible to obtain a laminated product that retains transparency and surface hardness.

The thermoplastic laminating material (B) preferably has a thickness of 0.05 mm to 5 mm, more preferably 0.1 mm to 1 mm, and a thickness of 0.125 mm to 0.125 mm. It is particularly preferred to use a thickness of 0.4 mm. By setting it as said thickness, the durability in protecting the surface of a molding (C) can be provided.

In addition, the thermoplastic bonding material (B) is optionally applied to the surface of the thermoplastic bonding material (B) by coating, transfer, co-extrusion, etc. for the purpose of preventing scratches on the surface and improving slipperiness. A hard coat layer, a mat layer, or the like may be laminated.

In addition, when the thermoplastic bonding material (B) is used for an article that is used outdoors such as the exterior of an automobile, the thermoplastic bonding material (B) and the heat-sensitive adhesive sheet (A ) or the molding (C), a layer absorbing ultraviolet rays having a wavelength of 325 nm to 380 nm may be provided on the surface or inside the thermoplastic bonding material (B) for the purpose of improving outdoor light resistance. As a method for forming the ultraviolet absorbing layer, a method of applying a coating agent or the like containing an arbitrary ultraviolet absorber or the like to the surface of the thermoplastic bonding material (B), or A method such as kneading an arbitrary ultraviolet absorber into the is exemplified. For the purpose of simplifying the process, it may be added to the hard coat layer, the mat layer, or the like before coating. In the case of the thermoplastic bonding material (B) containing the ultraviolet absorbing layer, the ultraviolet transmittance at a wavelength of 325 nm to 380 nm is preferably 0% to 20%, and 0% to 10% for imparting outdoor light resistance. is more preferred.

The thermoplastic bonding material (B) preferably has a light transmittance of 80% to 100% and a haze of 0% to 5.0% at a wavelength of 380 nm to 780 nm in the visible light region. It is more preferable to use one having a light transmittance of 85% to 100% at 380 nm to 780 nm and a haze of 0% to 2.0% or less. By setting it as the said range, the design property of the said laminated article can be improved.

The thermoplastic bonding material (B) is obtained by laminating a decorative layer and a functional layer in advance on the surface side on which the heat-sensitive adhesive sheet (A) is laminated, and ) in which the decorative layer and the functional layer are laminated between the heat adhesive sheets. The thickness of the decorative layer and the functional layer is preferably 35% or less, more preferably 25% or less, and particularly preferably 10% or less of the thickness of the heat-sensitive adhesive sheet. By setting the above range, the heat-sensitive adhesive layer (a) of the heat-sensitive adhesive sheet (A) is heated and laminated in the step of heating and laminating the thermoplastic laminating material (B). ) to eliminate steps and enhance the design of the laminated product.

The method for laminating the decorative layer and the functional layer may be any processing method, and a silk screen printer, a gravure printer, or the like is used to apply a colored paint, a metal-containing paint, or the like to the thermoplastic bonding material (B). A method of directly applying to the surface, a method of transferring to the surface of the thermoplastic bonding material (B) using a transfer foil on which a decorative layer or a functional layer is laminated in advance, or a method of spraying a colored paint or metal-containing paint A method of applying a paint containing, etc. to the surface of the thermoplastic bonding material (B), sputtering or plating the surface of the thermoplastic bonding material (B), or bonding a metal foil For example, a method of etching after the etching is performed.

A plurality of thermoplastic bonding materials (B) may be bonded together. When a plurality of thermoplastic bonding materials (B) are bonded together, the same type may be bonded together, or other types of materials listed in the above examples may be bonded together.

[Molded product (C)]
Examples of the molded article (C) to be bonded by the method of the present invention include, for example, molded articles having a decorative layer for the purpose of imparting design properties, light-shielding properties, and the like.

The molded article (C) may be a molded article formed by any molding method, for example, an insert molding method, a press molding method, or the like, and decorated by printing, painting, plating, or the like. It's okay. Also, the molding (C) may be of any shape and thickness.

Materials for the molded article (C) include inorganic materials such as glass and ceramics; metals such as stainless steel and aluminum; , polyimide, polyphenylene sulfide, polyphenylene ether, polypropylene, polyethylene, polystyrene, etc.; - It is preferable to use resin moldings such as alloys of styrene copolymers.

The molding (C) is obtained by laminating a decorative layer and a functional layer in advance on the surface side on which the heat-sensitive adhesive sheet (A) is laminated, and forming the heat-sensitive adhesive layer (a) and the molding (C). A heat adhesive sheet laminated with a decorative layer or a functional layer may be used. Such as the decorative layer and the functional layer. The thickness of each layer laminated on the surface side on which the heat-sensitive adhesive sheet (A) is laminated is preferably 35% or less, more preferably 25% or less, more preferably 10% of the thickness of the heat-sensitive adhesive sheet. The following thicknesses are particularly preferred. By setting the above range, in the step of laminating the heat-sensitive adhesive sheet (A) to the molded product (C), the decorative layer and the functional layer are the heat-sensitive adhesive layer (a) of the heat-sensitive adhesive sheet (A). It is possible to eliminate the step by burying it inside, and to improve the design of the laminated product.

The method for laminating the decorative layer and the functional layer may be any processing method, and a colored paint or metal-containing paint is directly applied to the surface of the molded article (C) using a silk screen printer, a gravure printer, or the like. a method of transferring to the surface of the molding (C) using a transfer foil on which a decorative layer or a functional layer has been laminated in advance, or a method of spray painting to apply a paint containing a colored paint, a metal-containing paint, etc. Examples include a method of coating the surface of the molding (C), a method of subjecting the surface of the molding (C) to a sputtering process A, a plating process, and a method of etching after laminating a metal foil.

A plurality of the moldings (C) may be laminated together. When a plurality of moldings (C) are to be laminated together, the same type may be laminated together, or other types of the above examples may be laminated together.

[Lamination method]
The method for producing the article of the present invention, that is, the method for producing an article in which the thermoplastic lamination material (B) and the molded article (C) are adhered and laminated with the heat-sensitive adhesive sheet (A), is -50 ° C. to The tensile loss tangent (tan δ) measured at a frequency of 3 Hz within the range of 200 ° C. has at least one peak temperature above 90 ° C. and at least one below -20 ° C., and tensile storage at 100 ° C. A heat-sensitive adhesive sheet (A) having a heat-sensitive adhesive layer (a) having an elastic modulus (E′ _a100 ) of 5×10 ⁵ Pa to 1×10 ⁸ Pa is used as an adhesive layer, and a thermoplastic laminate (B ) is heated to 90° C. to 200° C. and laminated to the surface of the molding (C).

The lamination method in the method for manufacturing the article is not particularly limited, but among them, the following step [1] and step [2] are performed in this order, and the following step [3] and step [4] are performed. A second mode in which the following steps [1] and steps [5] and [6] are performed in this order is preferable.

That is, the first aspect of the method for manufacturing the article is a step of bonding the heat-sensitive adhesive layer (a) of the heat-sensitive adhesive sheet (A) and the thermoplastic bonding material (B) to form a laminate. After [1] and the above step [1], the thermoplastic laminating material (B) or the heat-sensitive adhesive layer (a) is heated to 90 ° C. to 200 ° C., and the heat-sensitive adhesive layer ( A method for producing an article comprising a) and a step [2] of pressing and laminating the molded product (C) in this order. Two or more types of the thermoplastic bonding material (B) and the molding (C) may be simultaneously bonded in each step. The lamination processing of the thermoplastic lamination material (B) and the molding (C) by the molding machine described later is generally a batch production system, and can be one of the rate-limiting steps in the production process of the article. According to the method for manufacturing an article according to the first aspect, since the number of man-hours using a molding machine can be reduced, production efficiency is excellent.

In the first aspect, the heat-sensitive adhesive sheet (A) may have a release liner made of a thermoplastic resin material on one or both sides thereof. In this case, in step [1], if a release liner A is arranged on the surface of the heat-sensitive adhesive layer (a) to be laminated with the thermoplastic lamination material (B), the release liner A is peeled off. Step [1] is performed. In step [2], when a release liner B is arranged on the surface of the heat-sensitive adhesive layer (a) to be bonded to the molded article, the release liner B is peeled off and step [2] is carried out. .

In the step [1], the heat-sensitive adhesive sheet (A) has poor adhesiveness at room temperature, so it is preferable to temporarily bond the heat-sensitive adhesive layer (a) and the thermoplastic lamination material (B). Specifically, as a temporary adhesion method, a heat-sensitive adhesive layer of the heat-sensitive adhesive sheet (A) is laminated in a state in which a release liner is laminated on the opposite side of the heat-sensitive adhesive sheet (A) to the thermoplastic laminating material (B). A method of heat-adhering (a) and a thermoplastic lamination material (B) while passing them through a gap between a rotating rubber roller or a metal roller heated to 90° C. or higher, and a heat-sensitive adhesive layer (a) of the heat-sensitive adhesive sheet (A). ) and the thermoplastic laminating material (B) are temporarily laminated at room temperature without air bubbles, and then heated and cured in an atmosphere of 50° C. or higher for 24 hours or longer. . In this case, the heat-sensitive adhesive layer (a) and the thermoplastic laminating material (B) are permanently adhered during the step [2]. Further, in the step [2], the molding (C) is pressed against the surface of the heat-sensitive adhesive layer (a) with a molding machine at a pressure of about 0.1 MPa or more, or the thermoplastic laminating material (B ) is pressurized with compressed air of about 0.1 MPa or more, and the thermoplastic lamination material (B) and the heat-sensitive adhesive sheet (A) are deformed in a three-dimensional direction and attached to the surface of the molded product (C). is preferred.

In a second aspect of the method for manufacturing the article, the heat-sensitive adhesive layer (a) of the heat-sensitive adhesive sheet (A) is heated to 90° C. to 200° C., and the heat-sensitive adhesive layer of the heat-sensitive adhesive sheet (A) is After the step [3] of pressing and bonding (a) and the molded product (C) and the step [3], the thermoplastic bonding material (B) is heated to 90 ° C. to 200 ° C. , and a step [4] of pressing and laminating the thermoplastic lamination material (B) and the heat-sensitive adhesive layer (a), in this order. Two or more types of the thermoplastic bonding material (B) and the molding (C) may be simultaneously bonded in each step. According to the method for manufacturing an article of the second aspect, only the thermoplastic bonding material (B) capable of generating gas by heating is heated, and after the gas is released from the thermoplastic bonding material (B), the heat-sensitive bonding is performed. Since it is laminated with the sheet (A), it is possible to reduce swelling between the thermal adhesive layer (a) and the heat-sensitive adhesive layer (a) caused by gas generated from the thermoplastic lamination material (B).

Among them, in the second aspect of the method for manufacturing the article, a heat-sensitive adhesive sheet (A) laminated with a release liner made of a thermoplastic resin material is used, and the heat-sensitive adhesive sheet (A) is used together with the release liner. The heat-sensitive adhesive layer (a) of is heated to 90° C. to 200° C., and the surface of the heat-sensitive adhesive layer (a) of the heat-sensitive adhesive sheet (A) opposite to the surface on which the release liner is laminated and the After the step [3] of pressing and laminating the molding (C) and the step [3], the thermoplastic lamination material (B) is heated to 90 ° C. to 200 ° C., and the thermoplastic lamination is performed. It is preferable that the method for manufacturing an article includes the step [4] of pressurizing and laminating the material (B) and the heat-sensitive adhesive layer (a) after peeling and removing the release liner, in this order. Using a heat-sensitive adhesive sheet (A) laminated with a release liner made of a thermoplastic resin material, the heat-sensitive adhesive layer (a) was heated together with the release liner in step [3] to laminate the release liner. By laminating the molded product (C) in this state, the tensile strength of the heat-sensitive adhesive sheet (A) is increased, the heat-sensitive adhesive sheet (A) is easily pressed against the molded product (C), and the heat-sensitive adhesive layer ( This is because it is possible to prevent adhesion unevenness at the interface between a) and the molding (C) and air bubbles from entering the interface.

In the step [3], after heating the heat-sensitive adhesive sheet (A) in which a release liner made of a thermoplastic resin material is laminated on one side, the heat-sensitive adhesive layer (a) is ) The molding (C) is pressed against the surface, or the surface side of the thermoplastic release liner of the heat-sensitive adhesive sheet (A) is pressed to three-dimensionally move the heat-sensitive adhesive sheet (A) together with the release liner. It is preferable to apply to the surface of the molding (C) while deforming. This is because the adhesiveness to the surface of the deformed molded product (C) is improved, so that it can be adhered firmly.
The pressure when the molding (C) is pressed against the surface of the heat-sensitive adhesive layer (a) of the heat-sensitive adhesive sheet (A) after heating is preferably about 0.1 MPa or more. Alternatively, when pressing the thermoplastic release liner surface side of the heat-sensitive adhesive sheet (A), it is preferable to pressurize with compressed air of about 0.1 MPa or more.

In the step [4], the heat-sensitive adhesive layer (a) is pressed against the thermoplastic bonding material (B) with a pressure of about 0.1 MPa or more, or the surface side of the thermoplastic bonding material (B) is pressed. is compressed with compressed air of about 0.1 MPa or more to three-dimensionally deform the thermoplastic lamination material (B) while adhering it to the surface of the heat-sensitive adhesive layer (a).

Further, in the third aspect of the method for manufacturing the article, the heat-sensitive adhesive layer (a) of the heat-sensitive adhesive sheet (A) and the thermoplastic bonding material (B) are laminated in the same manner as in the first aspect. After the step [1] of combining to form a laminate and the above step [1], the thermoplastic laminating material (B) or the heat-sensitive adhesive layer (a) of the laminate is After the step [5] of heating to and pressing against a mold of the same type as the molded product (C) to mold the laminate into the shape of the molded product (C), and the above step [5], molding The surface of the molded product (C) is covered with the laminated product, and the heat-sensitive adhesive layer (a) is applied from at least one side of the thermoplastic laminate (B) or the molded product (C) at 90 ° C. A method for producing an article, comprising a step [6] of heating to 200° C. and laminating the heat-sensitive adhesive layer (a) and the molding (C) in this order. Two or more types of the thermoplastic lamination material (B) and the molding (C) may be laminated simultaneously in each step.
In the method for manufacturing an article according to the third aspect, the thermoplastic pasting material (B) laminated with the heat-sensitive adhesive sheet (A) is molded in advance to stabilize the shape, and heated to form the molded article (C). It is possible to reduce distortion caused by deformation of the thermoplastic lamination material (B) when laminating to the surface of , and to reduce lifting and peeling after lamination. In addition, since the heat-sensitive adhesive sheet of the present invention has low room-temperature adhesiveness, the thermoplastic lamination material (B) preliminarily molded into the shape of the molded article (C) is attached to the molded article (C) through the heat-sensitive adhesive sheet. ), and the thermoplastic lamination material (B) and the molded product (C) after molding can be closely bonded.

Examples of the molding machine used in the article manufacturing method include any molding machine such as a pressure molding machine, a vacuum molding machine, a TOM molding machine, an NGF molding machine, and a hot press molding machine. As an example of the bonding process of the first aspect by a molding machine, for example, a process of attaching the thermoplastic bonding material (B) laminated with the heat-sensitive adhesive sheet (A) through the process [1] and the molded product (C) to the molding machine. , the step of reducing the pressure in the tank in which the molding (C) is installed, and the step [1] of heating the thermoplastic laminate (B) laminated with the heat-sensitive adhesive sheet (A) at 90 ° C. to 200 ° C. After heating, the molding (C) is lifted and pressed against the heat-sensitive adhesive layer (a), and the thermoplastic laminate (B) laminated with the heat-sensitive adhesive sheet (A) is compressed by air pressure, a press plate, or the like. An article is manufactured through a step of applying pressure, a step of removing the laminated product from the molding machine, and trimming the thermoplastic laminated material (B) laminated with the heat-sensitive adhesive sheet (A) protruding from the molded product.

In addition, as an example of the attaching process of the second aspect by a molding machine, for example, a process of attaching a heat-sensitive adhesive sheet (A) having a release liner laminated on one side and a molding (C) to a molding machine, and setting the molding (C). a step of reducing the pressure in the bath, a step of heating the heat-sensitive adhesive sheet (A) with a release liner laminated on one side at 90° C. to 200° C., and a heat-sensitive adhesive layer ( A step of pressing against a) and pressing the heat-sensitive adhesive sheet (A) with a release liner laminated on one side with compressed air, a press plate, etc., removing the laminated product from the molding machine and removing the release liner protruding from the molded product A step of trimming the heat-sensitive adhesive sheet (A) laminated on one side, removing the release liner from the molded product (C) laminated with the heat-sensitive adhesive sheet (A), and molding together with the thermoplastic laminating material (B) The step of attaching to the machine, the step of reducing the pressure in the tank in which the molded product (C) laminated with the heat-sensitive adhesive sheet (A) is installed in the same manner as described above, and the thermoplastic laminating material (B) at 90 ° C. to 200 ° C. to press the heat-sensitive adhesive layer (a) against the thermoplastic bonding material (B), and press the thermoplastic bonding material (B) with air pressure or press. The article is manufactured through a step of applying pressure with a plate or the like, a step of removing the laminated product from the molding machine, and trimming the thermoplastic pasting material (B) protruding from the molded product.

As an example of the bonding process of the third aspect by a molding machine, for example, the thermoplastic bonding material (B) laminated with the heat-sensitive adhesive sheet (A) through the process [1] and the molded product (C) are attached to the molding machine. Thermoplastic lamination in which the heat-sensitive adhesive sheet (A) is laminated through the process, the process of reducing the pressure in the tank in which the mold of the same type as the molded product (C) having releasability on the surface is installed, and the process [1]. A step of heating the material (B) at 90 ° C. to 200 ° C., raising the mold after heating and pressing it against the heat-sensitive adhesive layer (a), and thermoplastic lamination in which the heat-sensitive adhesive sheet (A) is laminated. A step of pressing the material (B) with compressed air or a press plate, etc., removing the molded product of the thermoplastic laminating material (B) laminated with the heat-sensitive adhesive sheet (A) from the molding machine and laminating the heat-sensitive adhesive sheet (A) A step of trimming the thermoplastic laminating material (B), and a thermoplastic laminating material (B) in which the heat-sensitive adhesive sheet (A) is laminated on the surface of the molding (C) using a hot press device or the like. The article is manufactured through a step of press bonding while heating the thermoplastic laminate (B) or the molded product (C) laminated with the heat-sensitive adhesive sheet (A) at 90°C to 200°C.

The laminate bonded by the bonding method has a configuration in which the thermoplastic bonding material (B) and the molding (C) are laminated via the heat-sensitive adhesive sheet (A). Further, if necessary, the above-mentioned You may have the structure by which the decorative layer and the functional layer were laminated|stacked.

The laminated product obtained by the laminating method of the present invention is used for the exterior of home electric appliances, mobile terminals, and automobiles in which the decorative layer and the functional layer are laminated for the purpose of imparting design and functionality to the surface of the molded product. It is suitably used for resin moldings used for interior and exterior decoration. The molded product (C) is a three-dimensionally molded part by insert molding, press molding, or the like. , a thermoplastic lamination material (B) having a hard coat layer or a mat layer on the surface thereof is laminated by the method of the present invention. As a result, the laminated product obtained by the manufacturing method including the laminating method of the present invention is free from the formation of bubbles due to gas that can be generated from the surface of the molded product (C) and the surface of the thermoplastic laminated material (B), and the thermoplastic A laminated product that suppresses floating and peeling of the thermoplastic laminated material (B) caused by the repulsion of the curved surface of the laminated material (B), and has both excellent transparency and excellent appearance quality. It has become.

<Synthesis of block copolymer (k-1)>
1,240 parts by mass of dry toluene as a solvent was added to a reactor whose interior was degassed and replaced with nitrogen, and 52.0 parts by mass of 1,2-dimethoxyethane and isobutylbis(2,6-di-tert) were added while stirring. 60.0 parts by mass of a toluene solution containing 40.2 mmol of butyl-4-methylphenoxy)aluminum, and 5.17 parts by mass of a mixed solution of cyclohexane and n-hexane containing 2.98 mmol of sec-butyllithium as an anionic polymerization initiator. part, methyl methacrylate 54 . 0 parts by mass were added in this order and reacted at 25° C. for 1 hour. At this time, the polymerization conversion rate of methyl methacrylate was 99.5%. It was 9% or more. Next, the reaction solution was cooled to −30° C., 220.0 parts by mass of n-butyl acrylate was added dropwise over 2 hours, and after completion of dropwise addition, the mixture was stirred at −30° C. for 5 minutes. At this time, the polymerization conversion rate of n-butyl acrylate was 99.9%. It was 9% or more. Subsequently, 70.0 parts by mass of methyl methacrylate was added to this reaction solution, and after stirring overnight at 25° C., 3.50 g of methanol was added to terminate the polymerization reaction. The polymerization conversion rate of methyl methacrylate at this time was 99.9% or more. The obtained reaction solution is poured into a large amount of methanol, the filtrate is vacuum dried, and the polymer block (S2) having a glass transition temperature of 90° C. or higher contains 36% by mass of polymethyl methacrylate and is −20° C. or lower. A triblock copolymer ( k-1) was obtained. The weight average molecular weight (Mw) of the obtained triblock copolymer (k-1) was 82,000 as determined by GPC measurement by the method described above. Further, when the glass transition temperature (Tg) of each polymer block of the triblock copolymer (k-1) was measured, the Tg of the polymethyl methacrylate polymer block was 103°C, and that of the polyn-butyl acrylate was 103°C. The Tg of the polymer block was -51°C.

The glass transition temperature (Tg) of each polymer block of the block copolymer (k-1) was measured using a differential scanning calorimeter (“DSC-7020” manufactured by Hitachi High-Tech Science Systems Co., Ltd.). In the curve obtained by measuring from −100° C. to 150° C. at a temperature rate of 10° C./min, the extrapolated glass transition start temperature was taken as the glass transition temperature (Tg). The glass transition temperature (Tg) of each polymer block in block copolymers (k-2) to (k-8) and examples and comparative examples was also measured by the method described above.

<Synthesis of block copolymer (k-2)>
Polymethacrylic acid is used as a polymer block (S2) having a glass transition temperature of 90° C. or higher by adjusting the amount of methyl methacrylate and n-butyl acrylate used in the same manner as for the block copolymer (k-1). Polymethyl methacrylate-polyn-butyl acrylate containing 70% by mass of polyn-butyl acrylate as the polymer block (S1) containing 30% by mass of methyl and having a glass transition temperature of −20° C. or lower A triblock copolymer (k-2) composed of polymethyl methacrylate was obtained. The weight average molecular weight (Mw) of the resulting triblock copolymer (k-2) was 84,000 as determined by GPC measurement according to the method described above. Further, when the glass transition temperature (Tg) of each polymer block of the triblock copolymer (k-2) was measured, the Tg of the polymer block of polymethyl methacrylate was 103°C, and that of polyn-butyl acrylate was 103°C. The Tg of the polymer block was -52°C.

<Synthesis of block copolymer (k-3)>
Polymethacrylic acid is used as a polymer block (S2) having a glass transition temperature of 90° C. or higher by adjusting the amount of methyl methacrylate and n-butyl acrylate used in the same manner as for the block copolymer (k-1). Polymethyl methacrylate-polyn-butyl acrylate containing 60% by mass of polyn-butyl acrylate as the polymer block (S1) containing 40% by mass of methyl and having a glass transition temperature of −20° C. or lower A triblock copolymer (k-3) composed of polymethyl methacrylate was obtained. The weight average molecular weight (Mw) of the obtained triblock copolymer (k-3) was 79,000 as determined by GPC measurement according to the method described above. Further, when the glass transition temperature (Tg) of each polymer block of the triblock copolymer (k-3) was measured, the Tg of the polymer block of polymethyl methacrylate was 104°C, and that of polyn-butyl acrylate was 104°C. The Tg of the polymer block was -51°C.

<Synthesis of block copolymer (k-4)>
Polymethacrylic acid is used as a polymer block (S2) having a glass transition temperature of 90° C. or higher by adjusting the amount of methyl methacrylate and n-butyl acrylate used in the same manner as for the block copolymer (k-1). Polymethyl methacrylate-polyn-butyl acrylate containing 50% by mass of methyl and containing 50% by mass of polyn-butyl acrylate as the polymer block (S1) having a glass transition temperature of −20° C. or lower A triblock copolymer (k-4) composed of polymethyl methacrylate was obtained. The weight average molecular weight (Mw) of the resulting triblock copolymer (k-4) was 76,000 as determined by GPC measurement according to the method described above. Further, when the glass transition temperature (Tg) of each polymer block of the triblock copolymer (k-4) was measured, the Tg of the polymer block of polymethyl methacrylate was 104°C, and that of polyn-butyl acrylate was 104°C. The Tg of the polymer block was -52°C.

<Synthesis of block copolymer (k-5)>
Polymethacrylic acid is used as a polymer block (S2) having a glass transition temperature of 90° C. or higher by adjusting the amount of methyl methacrylate and n-butyl acrylate used in the same manner as for the block copolymer (k-1). Polymethyl methacrylate-polyn-butyl acrylate containing 73% by mass of polyn-butyl acrylate as the polymer block (S1) containing 27% by mass of methyl and having a glass transition temperature of −20° C. or lower A triblock copolymer (k-5) composed of polymethyl methacrylate was obtained. The weight average molecular weight (Mw) of the resulting triblock copolymer (k-5) was 83,000 as determined by GPC measurement according to the method described above. Further, when the glass transition temperature (Tg) of each polymer block of the triblock copolymer (k-5) was measured, the Tg of the polymer block of polymethyl methacrylate was 103°C, and that of polyn-butyl acrylate was 103°C. The Tg of the polymer block was -53°C.

<Synthesis of block copolymer (k-6)>
5,000 parts by mass of dry cyclohexane as a solvent and 2 parts by mass of a cyclohexane solution containing 10.5% by mass of sec-butyllithium as an anionic polymerization initiator were charged into a reactor whose interior was degassed and replaced with nitrogen, and a Lewis base was added. 28 parts by mass of tetrahydrofuran was charged. After raising the temperature to 50° C., 70 parts by mass of styrene was added and reacted for 1 hour. Subsequently, 345 parts by mass of butadiene was added and polymerized for 2 hours. Thus, a reaction liquid containing a polystyrene-polybutadiene-polystyrene triblock copolymer was obtained.
To this reaction solution, 10% by mass of palladium on carbon (amount of palladium supported: 5% by mass) was added as a hydrogenation catalyst relative to the block copolymer, and the reaction was carried out for 10 hours under conditions of a hydrogen pressure of 2 MPa and 150°C. .
After allowing to cool and release pressure, palladium carbon is removed by filtration, and the filtrate is concentrated and further vacuum-dried to obtain a polymer block (S2) having a glass transition temperature of 90°C or higher, containing 30% by mass of polystyrene. Pellets of a polystyrene-hydrogenated polybutadiene-polystyrene triblock copolymer (k-6) containing 70% by mass of hydrogenated polybutadiene as the polymer block (S1) having a glass transition temperature of −20° C. or lower are obtained. rice field. The weight average molecular weight (Mw) of the resulting triblock copolymer (k-6) was 200,000 as determined by GPC measurement according to the method described above. Further, when the glass transition temperature (Tg) of each polymer block of the triblock copolymer (k-6) was measured, the Tg of the polystyrene polymer block was 97°C, and the Tg of the hydrogenated polybutadiene polymer block was It was -23°C.

<Synthesis of block copolymer (k-7)>
The amount of styrene and butadiene used was adjusted in the same manner as the block copolymer (k-6), and 67% by mass of polystyrene was used as a hard block (polymer block (S2) having a glass transition temperature of 90 ° C. or higher). to obtain a polystyrene-hydrogenated polybutadiene-polystyrene triblock copolymer (k-7) containing 33% by mass of hydrogenated polybutadiene as the polymer block (S1) having a glass transition temperature of −20° C. or lower rice field. The weight average molecular weight (Mw) of the resulting triblock copolymer (k-7) was 100,000 as determined by GPC measurement according to the method described above. Further, when the glass transition temperature (Tg) of each polymer block of the triblock copolymer (k-7) was measured, the Tg of the polystyrene polymer block was 98°C, and the Tg of the hydrogenated polybutadiene polymer block was It was -23°C.

<Synthesis of acrylic random copolymer (k-8)>
50 parts by mass of n-butyl acrylate, 30 parts by mass of methyl methacrylate, 20 parts by mass of 2-hydroxyethyl methacrylate, and polymerization Dissolve 0.5 parts by mass of 2,2'-azobisisobutylnitrile as an initiator in 150 parts by mass of ethyl acetate, replace with nitrogen, and polymerize at 80 ° C. for 8 hours to obtain a (meth)acrylic random copolymer (k -8) was obtained. The weight average molecular weight (Mw) of the obtained (meth)acrylic random copolymer (k-8) was 470,000 as determined by GPC measurement according to the method described above. Further, when the glass transition temperature (Tg) of the (meth)acrylic random copolymer (k-8) was measured, no inflection point was observed.

<Synthesis of acrylic random copolymer (k-9)>
80 parts by mass of methyl methacrylate, 15 parts by mass of ethyl acrylate, 5 parts by mass of 2-hydroxyethyl acrylate and a polymerization initiator were placed in a reaction vessel equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen gas inlet. Dissolve 0.7 parts by mass of 2,2'-azobisisobutylnitrile in 150 parts by mass of ethyl acetate as a solution, replace with nitrogen, and polymerize at 85 ° C. for 10 hours to obtain a (meth) acrylic random copolymer (k-9 ) was obtained. The weight average molecular weight (Mw) of the obtained (meth)acrylic random copolymer (k-9) was 220,000 as determined by GPC measurement according to the method described above. Further, when the glass transition temperature (Tg) of the (meth)acrylic random copolymer (k-9) was measured, the Tg was 72°C.

(Example 1)
<Preparation of heat-sensitive adhesive sheet (A-1)>
135 parts by mass of the triblock copolymer (k-1) was dissolved in 165 parts by mass of toluene with stirring to obtain a solution of adhesive composition (a-1) having a solid content of 45% by mass. The content of the polymer block (S2) having a glass transition temperature of 90°C or higher in the triblock copolymer is 36 parts by mass, and the content of the polymer block (S1) having a glass transition temperature of -20°C or lower is 64% by mass.
As the release liner A on the heavy release side, a 75 μm thick polyethylene terephthalate film (“TN100-75 μm” manufactured by Toyobo Co., Ltd.) whose one side was release-treated with a non-silicone compound was coated on the release-treated surface with a thickness of The adhesive composition (a-1) was applied to a thickness of 100 μm, dried at 70° C. for 3 minutes and 120° C. for 4 minutes, and released on one side with a silicone compound as release liner B on the light release side. A heat-sensitive adhesive sheet (A-1) was produced by laminating the release-treated surface of a polyethylene terephthalate film (“50E-0010BD” manufactured by Fujimori Industry Co., Ltd.) having a thickness of 50 μm.

(Example 2)
<Preparation of heat-sensitive adhesive sheet (A-2)>
54 parts by mass of the triblock copolymer (k-2) and 81 parts by mass of the triblock copolymer (k-3) are stirred and dissolved in 156 parts by mass of toluene to prepare an adhesive composition (a -2) was obtained. The average content of the polymer block (S2) having a glass transition temperature of 90°C or higher in the triblock copolymer is 36% by mass, and the content of the polymer block (S1) having a glass transition temperature of -20°C or lower. was an average of 64% by mass. In addition, the polymer block (S1) in the block copolymer mixture of the triblock copolymer (k-2) and the triblock copolymer (k-3) in the adhesive composition (a-2), ( The contents of S2) are the polymer blocks (S1) and (S2) in the block copolymer mixture described in the section "Heat-sensitive adhesive layer (a)" in "1. Heat-sensitive adhesive sheet (A)" above. ) was calculated based on the formula (1) of the content rate.
The thickness after drying is 100 μm in the same manner as in Example 1 except that the solution of the adhesive composition (a-2) is used instead of the solution of the adhesive composition (a-1). Thus, a heat-sensitive adhesive sheet (A-2) was produced.

(Example 3)
<Preparation of heat-sensitive adhesive sheet (A-3)>
122 parts by mass of the triblock copolymer (k-3) and 13 parts by mass of Pine Crystal KE-311 (manufactured by Arakawa Chemical Industries, Ltd., ultra-light rosin derivative) as a tackifier were stirred and dissolved in 156 parts by mass of toluene. , to obtain a solution of the adhesive composition (a-3) having a solid content of 45% by mass. The content of the polymer block (S2) having a glass transition temperature of 90°C or higher in the triblock copolymer is 40% by mass, and the content of the polymer block (S1) having a glass transition temperature of -20°C or lower is 60% by mass.
The thickness after drying is 100 μm in the same manner as in Example 1 except that the solution of the adhesive composition (a-3) is used instead of the solution of the adhesive composition (a-1). Thus, a heat-sensitive adhesive sheet (A-3) was produced.

(Example 4)
<Preparation of heat-sensitive adhesive sheet (A-4)>
54 parts by mass of the triblock copolymer (k-2) and 81 parts by mass of the triblock copolymer (k-4) are stirred and dissolved in 156 parts by mass of toluene to prepare an adhesive composition (a -4) was obtained. The average content of the polymer block (S2) having a glass transition temperature of 90°C or higher in the triblock copolymer is 42% by mass, and the content of the polymer block (S1) having a glass transition temperature of -20°C or lower. was 58% by mass. In addition, the polymer block (S1) in the block copolymer mixture of the triblock copolymer (k-2) and the triblock copolymer (k-4) in the adhesive composition (a-4), ( The contents of S2) are the polymer blocks (S1) and (S2) in the block copolymer mixture described in the section "Heat-sensitive adhesive layer (a)" in "1. Heat-sensitive adhesive sheet (A)" above. ) was calculated based on the formula (1) of the content rate.
The thickness after drying is 100 μm in the same manner as in Example 1 except that the solution of the adhesive composition (a-4) is used instead of the solution of the adhesive composition (a-1). Thus, a heat-sensitive adhesive sheet (A-4) was produced.

(Example 5)
<Preparation of heat-sensitive adhesive sheet (A-5)>
135 parts by mass of the triblock copolymer (k-2) was dissolved in 156 parts by mass of toluene with stirring to obtain a solution of adhesive composition (a-5) having a solid content of 45% by mass. The average content of the polymer block (S2) having a glass transition temperature of 90°C or higher in the triblock copolymer is 30% by mass, and the content of the polymer block (S1) having a glass transition temperature of -20°C or lower. was 70% by mass on average.
The thickness after drying is 100 μm in the same manner as in Example 1 except that the solution of the adhesive composition (a-5) is used instead of the solution of the adhesive composition (a-1). Thus, a heat-sensitive adhesive sheet (A-5) was produced.

(Example 6)
<Preparation of heat-sensitive adhesive sheet (A-6)>
Separately from the preparation of the heat-sensitive adhesive sheet (A-1) of Example 1, on the release-treated surface of the release liner B (polyethylene terephthalate film "50E-0010BD") used in Example 1, the thickness after drying was applied. is 100 μm, the solution of the adhesive composition (a-1) is applied, dried at 70 ° C. for 3 minutes and 120 ° C. for 4 minutes, and the previously prepared heat-sensitive adhesive sheet (A-1 ), and then a heat laminator (manufactured by Tester Sangyo Co., Ltd., "SA-1010 small desktop test laminator" heated to 120 ° C. at a speed of 1 m / min and a pressure of 0.2 MPa. The adhesive layers were adhered to prepare a heat-sensitive adhesive sheet (A-6) having an adhesive layer thickness of 200 μm.

(Example 7)
<Preparation of heat-sensitive adhesive sheet (A-7)>
A heat-sensitive adhesive sheet ( A-7) was produced.

(Example 8)
<Preparation of heat-sensitive adhesive sheet (A-8)>
An adhesive composition (a -8) was obtained. The content of the polymer block (S2) having a glass transition temperature of 90°C or higher in the triblock copolymer was 37.4% by mass on average, and the content of the polymer block (S1) having a glass transition temperature of -20°C or lower was 37.4% by mass on average. The content was 62.6% by mass on average. In addition, the polymer block (S1) in the block copolymer mixture of the triblock copolymer (k-6) and the triblock copolymer (k-7) in the adhesive composition (a-8), ( The contents of S2) are the polymer blocks (S1) and (S2) in the block copolymer mixture described in the section "Heat-sensitive adhesive layer (a)" in "1. Heat-sensitive adhesive sheet (A)" above. ) was calculated based on the formula (1) of the content rate.
The thickness after drying is 100 μm in the same manner as in Example 1 except that the solution of the adhesive composition (a-8) is used instead of the solution of the adhesive composition (a-1). Thus, a heat-sensitive adhesive sheet (A-8) was produced.

(Example 9)
<Preparation of heat-sensitive adhesive sheet (A-13)>
122 parts by mass of the triblock copolymer (k-1) and 13 parts by mass of YS Polystar TH130 (manufactured by Yasuhara Chemical Co., Ltd., terpene phenolic resin) as a tackifier were dissolved in 156 parts by mass of toluene with stirring, and the solid content was 45 masses. % solution of adhesive composition (a-13) was obtained. The content of the polymer block (S2) having a glass transition temperature of 90°C or higher in the triblock copolymer is 36% by mass, and the content of the polymer block (S1) having a glass transition temperature of -20°C or lower is 64% by mass.
A heat-sensitive adhesive sheet (A-13) was prepared in the same manner as in Example 1 so that the thickness after drying was 100 μm.

(Comparative example 1)
<Preparation of heat-sensitive adhesive sheet (A-9)>
135 parts by mass of the triblock copolymer (k-5) was dissolved in 156 parts by mass of toluene with stirring to obtain a solution of adhesive composition (a-9) having a solid content of 45% by mass. The content of the polymer block (S2) having a glass transition temperature of 90°C or higher in the triblock copolymer was 27% by mass, and the content of the polymer block (S1) having a glass transition temperature of -20°C or lower was It became 73% by mass.
The thickness after drying is 100 μm in the same manner as in Example 1 except that the solution of the adhesive composition (a-9) is used instead of the solution of the adhesive composition (a-1). Thus, a heat-sensitive adhesive sheet (A-9) was produced.

(Comparative example 2)
<Preparation of heat-sensitive adhesive sheet (A-10)>
135 parts by mass of the triblock copolymer (k-4) was dissolved in 156 parts by mass of toluene with stirring to obtain a solution of adhesive composition (a-10) having a solid content of 45% by mass. The content of the polymer block (S2) having a glass transition temperature of 90°C or higher in the triblock copolymer is 50% by mass, and the content of the polymer block (S1) having a glass transition temperature of -20°C or lower is 50% by mass.
The thickness after drying is 100 μm in the same manner as in Example 1 except that the solution of the adhesive composition (a-10) is used instead of the solution of the adhesive composition (a-1). Thus, a heat-sensitive adhesive sheet (A-10) was produced.

(Comparative Example 3)
<Preparation of heat-sensitive adhesive sheet (A-11)>
To 100 parts by mass of the solid content of the acrylic copolymer resin (k-8), 5 parts by mass of Coronate HXR (manufactured by Tosoh Industry Co., Ltd., solid content 100% by mass) as an isocyanurate cross-linking agent is added, and a stirrer is added. and stirred for 20 minutes to obtain a solution of adhesive composition (a-11) having a solid content of 43% by mass.
The thickness after drying is 100 μm in the same manner as in Example 1 except that the solution of the adhesive composition (a-11) is used instead of the solution of the adhesive composition (a-1). Then, it was left in an atmosphere of 40° C. for 5 days to prepare a heat-sensitive adhesive sheet (A-11).

(Comparative Example 4)
<Preparation of pressure-sensitive adhesive sheet (A-12)>
A commercially available acrylic pressure-sensitive adhesive sheet having a thickness of 50 μm (manufactured by DIC Corporation, “Ditac ZB7012W”) was used. The pressure-sensitive adhesive sheet has a laminated structure of light release liner/acrylic pressure-sensitive adhesive layer/heavy release liner.

(Comparative Example 5)
<Production of heat-sensitive adhesive sheet (A-14)>
For 100 parts by mass of the solid content of the (meth)acrylic random copolymer resin (k-9), 2.5 parts by mass of Coronate HXR (manufactured by Tosoh Corporation, solid content 100 mass%) as an isocyanurate-based cross-linking agent. By adding and stirring with a stirrer for 20 minutes, a solution of adhesive composition (a-14) having a solid content of 42% by mass was obtained.
The thickness after drying is 100 μm in the same manner as in Example 1 except that the solution of the adhesive composition (a-14) is used instead of the solution of the adhesive composition (a-1). Then, it was left in an atmosphere of 40° C. for 5 days to prepare a heat-sensitive adhesive sheet (A-14).

<Preparation of thermoplastic lamination material (B-1)>
A commercially available polycarbonate sheet having a thickness of 0.3 mm ("Panlite PC-2151" manufactured by Teijin Limited) was cut into a size suitable for each evaluation and used.

<Preparation of thermoplastic laminating material (B-2)>
A commercially available polycarbonate sheet with a thickness of 0.125 mm (manufactured by Teijin Limited, "Panlite PC-2151") was cut into a size suitable for each evaluation and used.

<Preparation of molding (C-1)>
A commercially available polycarbonate molded article having a thickness of 3 mm ("Polycarbonate ECK100UU" manufactured by Teijin Limited, manufactured by Sumitomo Bakelite Co., Ltd.) was cut into a size suitable for each evaluation and used.

(Method for measuring tensile storage modulus and loss tangent)
The release liners were sequentially removed from the adhesive sheets obtained in Examples and Comparative Examples, and the sheets were laminated to a thickness of 600 μm, and then left in a drier at 120° C. for 30 seconds to heat-sensitively bond each layer. A rectangular test piece was prepared by cutting the width of 5 mm, the length of the measuring part to 20 mm, and the handle length of 20 mm at each end. The release liner on both sides was peeled off, and a tensile dynamic viscoelasticity measuring device (manufactured by TA Instruments, RSA III) was used to measure the temperature at a temperature rise rate of 5 ° C./min, a measurement frequency of 3.0 Hz, and a measurement temperature range of - Tensile storage modulus (E' _a-20 , E' _a25 , E' _a100 , E' _a150 ) and loss tangent at −20° C., 25° C., 100° C. and 150° C. respectively, measured in the range of 50 to 200° C. (tan δ) was measured. From the obtained loss tangent (tan δ) graph, the presence or absence of a peak temperature, its temperature, and the loss tangent (tan δ) at the peak temperature were read.

(Method for evaluating foaming resistance and peeling resistance during lamination)
The adhesive sheets obtained in the above Examples and Comparative Examples were cut into a size of 30 cm square, and the release liner B (PET film "50E-0010BD)" of the adhesive sheets of Examples 1 to 9 and Comparative Examples 1 to 3 and 5 was used. Alternatively, the release liner on the light release side of the adhesive sheet used in Comparative Example 4 is removed, temporarily laminated to a thermoplastic lamination material (B-1) of the same size with a hand roller, and then heated to 120 ° C. The adhesive sheet was heat-sensitively adhered to the thermoplastic laminating material (B-1) through a laminator ("SA-1010 compact desktop test laminator" manufactured by Tester Sangyo Co., Ltd.) at a speed of 1 m/min and a pressure of 0.2 MPa.
Next, the sample was cut into 10 cm squares, the release liner on the remaining one side was removed, placed on the surface of a molded product (C-1) with a size of 12 cm squares, and a heat press device (Tester Sangyo Co., Ltd. hot press Machine "TP-750 Air Press"), only the surface side of the thermoplastic laminating material (B-1) is heated at 140 ° C. for 15 seconds at a pressure of 0.2 MPa, and the sample is molded (C-1 ) to obtain a laminate.
Although Comparative Example 4 is a pressure-sensitive adhesive sheet, a laminate was produced under the same conditions as described above. In the following evaluations, unless otherwise specified, the laminates were prepared and used under the same conditions as those of other examples and comparative examples.
The appearance of the obtained laminated product was visually evaluated according to the following criteria.

<Evaluation of foaming resistance and peeling resistance during lamination>
⊚: No minute air bubbles or peeling was observed.
◯: There were very few fine air bubbles or peeling, but the appearance was at a level of no problem.
x: There were air bubbles or peeling, and the appearance was poor.

(Method for evaluating foaming resistance and peeling resistance after being left in a hot and humid environment)
The patch was continuously left for 250 hours in an environment with a temperature of 85° C. and a relative humidity of 85% RH.
<Evaluation of foaming resistance and peeling resistance after leaving in a hot and humid environment>
⊚: There was no increase in fine air bubbles or peeling compared to before standing.
◯: There was a slight increase in fine air bubbles or peeling compared to before standing, but the level was satisfactory in terms of appearance.
x: Compared to before standing, air bubbles or peeling increased, and the appearance was poor.

(Method for evaluating foaming resistance and peeling resistance after being left in a cold environment)
After repeating the condition of leaving the patch for 30 minutes in an environment at a temperature of −20° C. and then for 30 minutes in an environment at a temperature of 85° C. for 250 times, the appearance of the patch after being left in the hot and humid environment is observed. Visual evaluation was performed according to the same criteria as the method for evaluating foaming resistance and peeling resistance.

(Method for evaluating domain size of polymer block (S2))
In the phase mode of a scanning probe microscope (SPM), an arbitrary portion of the adhesive surface of the adhesive sheets obtained in the above examples and comparative examples was scanned in a field of view of 1 μm. The morphology was visually confirmed. In addition, the length of the long side of the domain formed by the polymer block (S2) at arbitrary 5 points or more was measured and averaged to determine the size of the domain of the polymer block (S2). "Nano-DST" manufactured by Pacific Nanotechnology was used as a scanning probe microscope, and measurements were made in the close contact mode.

(Method for evaluating peel adhesive strength immediately after application)
The adhesive sheets obtained in Examples and Comparative Examples were cut into a size of 30 cm square, and the release liner B (PET film "50E-0010BD)" of the adhesive sheets of Examples 1 to 9 and Comparative Examples 1 to 3, 5 or The release liner on the light release side of the adhesive sheet used in Comparative Example 4 was removed, and the adhesive sheet was temporarily laminated to a thermoplastic lamination material (B-2) of the same size with a hand roller, and then heated to 120 ° C. It was passed through a laminator at a speed of 1 m/min and a pressure of 0.2 MPa to heat-sensitively bond the adhesive sheet to the thermoplastic lamination material (B-2).
Next, the sample was cut to a width of 1 cm and a length of 10 cm, and the release liner on the remaining one side was removed in an environment of a temperature of 23° C. and a relative humidity of 50% RH, and the sample was cut into a size of 2 cm in width and 12 cm in length. Placed on the surface of the molded product (C-1), pressurized once with a 2 kg roller, and within 1 minute with a Tensilon type tensile tester (RTG-1210, manufactured by A&D Co., Ltd.) equipped with a constant temperature bath. The peel resistance was measured when the thermoplastic laminate (B-2) laminated with the adhesive sheet was pulled in the direction of 180° at a pulling speed of 50 mm/min under the above environment.
In the case of peeling due to the stick-slip phenomenon, the average value of each intermittent peeling resistance peak was taken as the peeling adhesive strength.

(Method for evaluating peel adhesive strength after heat bonding)
Cut into 1 cm wide and 10 cm long in the same manner as in the evaluation of the peel adhesive strength immediately after application, remove the release liner on the remaining one side under an environment of 23 ° C. and 50% relative humidity, After placing it on the surface of the molded product (C-1) cut to a length of 12 cm, it is set in the heat press device, and only the surface side of the thermoplastic bonding material (B-2) is pressed at 0.2 MPa. and heated at 140° C. for 15 seconds to heat-sensitively adhere the sample to the surface of the molding (C-1) to obtain a laminate. The peeling resistance of the obtained laminate was measured in an atmosphere of 23° C. after heat bonding in the same manner as the evaluation of the peeling adhesive strength immediately after bonding. A laminated product was prepared in the same manner as described above, and the peel resistance was measured under a temperature environment of 90°C and a temperature of -20°C.
In the case of peeling due to the stick-slip phenomenon, the average value of each intermittent peeling resistance peak was taken as the peeling adhesive strength.

(Method for evaluating embeddability of metal wire)
The adhesive sheets obtained in the above Examples and Comparative Examples were cut into a size of 30 cm square, and the release liner B (PET film "50E-0010BD)" of the adhesive sheets of Examples 1 to 9 and Comparative Examples 1 to 3 and 5 was used. Alternatively, the release liner on the light release side of the adhesive sheet used in Comparative Example 4 is removed, temporarily laminated to a thermoplastic lamination material (B-1) of the same size with a hand roller, and then heated to 120 ° C. The sheet was passed through a thermal laminator at a speed of 1 m/min and a pressure of 0.2 MPa to adhere the heat-sensitive adhesive sheet to the thermoplastic lamination material (B-1).
Next, the sample was cut into 10 cm squares, the release liner on the remaining one side was removed, and a polyurethane copper wire with a diameter of 0.2 mm (manufactured by Sanko Densho Co., Ltd., UEW) cut to a length of 12 cm was applied to the surface of the adhesive layer. Five pieces are placed at equal intervals, and heated at 140 ° C. for 15 seconds at a pressure of 0.2 MPa with the heat press device from the side of the thermoplastic bonding material (B-1) to form the thermoplastic bonding material (B-1). The reduced thickness of the portion where the adhesive sheet and the metal wire were laminated was measured, and the embedding rate was calculated according to the following criteria. Furthermore, when the embedding rate exceeded 25%, it was rated as ◯, and when it did not exceed 25%, it was rated as x.
Embedding rate [%] = reduced thickness before and after hot pressing [μm] / thickness of adhesive sheet [μm] × 100

(Evaluation method for ease of correction of pasting position)
The adhesive sheets obtained in Examples and Comparative Examples were cut to a size of 30 cm square, the release liner was removed on one side, and the thermoplastic laminating material (B-2) of the same size was temporarily laminated with a hand roller. Then, it was passed through the thermal laminator heated to 120° C. at a speed of 1 m/min and a pressure of 0.2 MPa to thermally bond the adhesive sheet to the thermoplastic lamination material (B-2).
Next, it is cut into a size of 5 cm square, placed on a bright annealed SUS304 stainless steel plate with a thickness of 1 mm in an environment of a temperature of 23 ° C. and a relative humidity of 50% RH, and a 2 kg roller is used at 300 mm / min. Pressurized one reciprocating speed. After 1 minute, it was peeled off by hand in the direction of 90° at a speed of about 1 m/min, and the ease of correcting the bonding position was evaluated by peeling off the thermoplastic bonding material (B-2) laminated with the adhesive sheet. Evaluate ease.

<Evaluation of ease of correction of pasting position>
A: Easy to peel, and no deformation of the thermoplastic lamination material (B-2) was observed.
◯: Slightly heavy peeling, but no deformation of the thermoplastic laminating material (B-2) was observed. x: Detachment was severe, and deformation of the thermoplastic laminating material (B-2) was observed.

(Measurement method of total light transmittance Tt and haze)
The total light transmittance Tt and haze were determined by removing the release liners on both sides of the adhesive sheets obtained in Examples and Comparative Examples, and measuring the total light transmittance Tt and haze by Murakami Color Research Laboratory Co., Ltd. ” was used to measure.

In the heat-sensitive adhesive sheets obtained in Examples 1 to 9, in the step of heating the thermoplastic bonding material laminated with the heat-sensitive adhesive sheet to 140 ° C. and bonding it to the surface of the molded product, Formation of bubbles due to possible gases and peeling of the thermoplastic lamination material are suppressed, and the lamination product has an excellent appearance. In addition, even if these laminated products are left in a hot and humid environment, formation of air bubbles and peeling due to gas that can be generated from at least one of the thermoplastic laminated product and the molded product is suppressed, and furthermore, an environment where cold and heat are repeated. Even when left for a long period of time, lifting and peeling between the thermoplastic laminating material and the molding are suppressed, and an excellent appearance can be maintained.
On the other hand, in the heat-sensitive adhesive sheets and the pressure-sensitive adhesive sheets obtained in Comparative Examples 1, 3, and 4, the tensile storage elastic modulus at 100°C was below the specified range, indicating that the thermoplastic laminating materials laminated with the adhesive sheets In the process of heating to 140 ° C. and laminating it to the surface of the molded product, the formation of bubbles due to the gas that can be generated from the thermoplastic laminating material and the peeling of the thermoplastic laminating material occur, and the lamination is inferior in appearance. It has become a thing. In addition, the heat-sensitive adhesive sheet obtained in Comparative Example 2 had a tensile storage elastic modulus at 100°C exceeding the specified range, and although no air bubbles were formed in the lamination step, it was left in an environment where cold and heat were repeated. Formation of air bubbles and peeling occurred when the laminate was applied, resulting in a laminate with an inferior appearance. The heat-sensitive adhesive sheet obtained in Comparative Example 5 has a tensile storage modulus at 100°C within the specified range, but has a peak temperature of the tensile loss tangent (tan δ) in a temperature range of -20°C or lower. When the laminate was left in an environment where cold and heat were repeated, air bubbles were formed and the laminate was peeled off, resulting in a laminate with an inferior appearance.

1 domain of polymer block (S1) 2 domain of polymer block (S2)

Claims (11)

Has at least one peak temperature of tensile loss tangent (tan δ) measured at a frequency of 3 Hz within the range of -50 ° C to 200 ° C at 90 ° C or higher and at least one at -20 ° C or lower, and 100 a heat-sensitive adhesive layer (a) having a tensile storage modulus (E′ _a100 ) at °C of 5×10 ⁵ Pa to 1×10 ⁸ Pa;
The heat-sensitive adhesive layer (a) comprises a block copolymer having a polymer block (S1) having a glass transition temperature of −20° C. or lower and a polymer block (S2) having a glass transition temperature of 90° C. or higher. containing, the content of the polymer block (S2) in the block copolymer is 29% by mass to 49% by mass,
In the block copolymer, the polymer block (S1) is at least one selected from the group consisting of methacrylic acid ester, acrylic acid ester, butadiene, hydrogenated butadiene, isobutene, and hydrogenated isobutene. wherein the polymer block (S2) is a polymer block made of at least one selected from the group consisting of methacrylic acid esters, acrylic acid esters, and styrene;
The combination of the polymer block (S1) and the polymer block (S2) of the block copolymer is
The polymer block (S1) is a polymer block comprising at least one of methacrylate and acrylic ester, and the polymer block (S2) is a polymer comprising at least one of methacrylate and acrylic ester. is a block,
or,
The polymer block (S1) is a polymer block made of at least one selected from the group consisting of butadiene, a hydrogenated product of butadiene, isobutene, and a hydrogenated product of isobutene, and the polymer block (S2) is styrene. is a polymer block of
A heat-sensitive adhesive sheet used for laminating a thermoplastic lamination material (B) to the surface of a molding (C) using the heat-sensitive adhesive layer (a) as an adhesive layer. 2. The content of the tackifier in the heat-sensitive adhesive layer (a) is 0 parts by weight, or 1 part to 30 parts by weight with respect to 100 parts by weight of the total amount of the block copolymer. heat-sensitive adhesive sheet. The heat-sensitive adhesive layer (a) is a block copolymer in which the polymer block (S1) is made of polyn-butyl acrylate and the polymer block (S2) is made of polymethyl methacrylate as the block copolymer. 3. The polymer according to claim 1 or 2, containing a polymer or a block copolymer in which the polymer block (S1) consists of hydrogenated polybutadiene and the polymer block (S2) consists of polystyrene. Thermal adhesive sheet. Claims 1 to 3, wherein the heat-sensitive adhesive layer (a) contains a block copolymer having an average domain size of 160 nm or more formed by polymer blocks (S2) having a glass transition temperature of 90°C or more. The heat-sensitive adhesive sheet according to any one of the items. The heat-sensitive adhesive sheet according to any one of claims 1 to 4, wherein the heat-sensitive adhesive layer (a) has a thickness in the range of 10 µm to 300 µm. The heat-sensitive adhesive sheet according to any one of claims 1 to 5, wherein the thermoplastic lamination material (B) has a thickness of 0.05 mm to 5 mm. At least one of the thermoplastic laminate (B) and the molded product (C) is an adherend capable of generating gas when left for 24 hours in an environment with a temperature of 85° C. and a relative humidity of 85% RH. The heat-sensitive adhesive sheet according to any one of claims 1 to 6. Between the heat-sensitive adhesive layer (a) and the thermoplastic laminate (B), or between the heat-sensitive adhesive layer (a) and the molding (C), the thickness of the heat-sensitive adhesive sheet is 35%. 8. The heat-sensitive adhesive sheet according to any one of claims 1 to 7, wherein a decorative layer or metal processing layer having a thickness of 10% or less is laminated. A method for producing an article in which the thermosensitive adhesive layer (a) of the thermosensitive adhesive sheet according to any one of claims 1 to 8 is used as an adhesive layer and the thermoplastic laminating material (B) is laminated on the surface of the molded article (C),
a step [1] of laminating the heat-sensitive adhesive layer (a) of the heat-sensitive adhesive sheet and the thermoplastic lamination material (B) to form a laminate;
After the step [1], the thermoplastic lamination material (B) or the heat-sensitive adhesive layer (a) is heated to 90 ° C. to 200 ° C., and the heat-sensitive adhesive layer (a) of the laminate and the molding A method for producing an article, comprising the step [2] of pressing and laminating the article (C). A method for producing an article in which the thermosensitive adhesive layer (a) of the thermosensitive adhesive sheet according to any one of claims 1 to 8 is used as an adhesive layer and the thermoplastic laminating material (B) is laminated on the surface of the molded article (C),
The heat-sensitive adhesive layer (a) of the heat-sensitive adhesive sheet is heated to 90° C. to 200° C., and the heat-sensitive adhesive layer (a) of the heat-sensitive adhesive sheet (A) and the molding (C) are pressed together. a step [3] of laminating with
After the step [3], the thermoplastic bonding material (B) is heated to 90° C. to 200° C., and the thermoplastic bonding material (B) and the heat-sensitive adhesive layer (a) are pressed together. A method for manufacturing an article, comprising the step [4] of laminating. A method for producing an article in which the thermosensitive adhesive layer (a) of the thermosensitive adhesive sheet according to any one of claims 1 to 8 is used as an adhesive layer and the thermoplastic laminating material (B) is laminated on the surface of the molded article (C),
a step [1] of laminating the heat-sensitive adhesive layer (a) of the heat-sensitive adhesive sheet and the thermoplastic lamination material (B) to form a laminate;
After the step [1], the thermoplastic lamination material (B) or the heat-sensitive adhesive layer (a) of the laminate is heated to 90 ° C. to 200 ° C., and the mold of the same type as the molded product (C) is heated. A step [5] of pressing against a frame and molding the laminate into the shape of the molding (C);
The surface of the molded product (C) is covered with the molded laminate, and the heat-sensitive adhesive layer (a) is heated at 90° C. from at least one side of the thermoplastic laminating material (B) or the molded product (C). A method for producing an article, comprising a step [6] of heating to 200° C. and laminating the heat-sensitive adhesive layer (a) and the molding (C).

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